Batrene
Business i?f Innovation
Environmental Technology
Verification Program
Advanced Monitoring
Systems Center
Test/QA Plan for Verification of
Nitrate Sensors for Groundwater
Remediation Monitoring
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ETV TEST/QA PLAN
for
Verification of Nitrate Sensors for
Groundwater Remediation Monitoring
April 23, 2010
Prepared by
Battelle
505 King Avenue
Columbus, OH 43201-2693
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SECTION A
PROJECT MANAGEMENT
Al Vendor Approval Page
ETV Advanced Monitoring Systems Center
Draft Test/QA Plan
for
Verification of Nitrate Sensors for
Groundwater Remediation Monitoring
April 23, 2010
VENDOR ACCEPTANCE
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Name
Company
Date
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A2 TABLE OF CONTENTS
Section Page
A PROJECT MANAGEMENT 3
Al Vendor Approval Page 3
A2 Table of Contents 4
A3 Acronyms and Abbreviations 7
A4 Distribution List 8
A5 Verification Test Organization 9
A5.1 Battelle 9
A5.2 Nitrate Sensor Vendors 12
A5.3 USD A ARS National Laboratory for Agriculture and the Environment,
Soil Microbiology and Environmental Quality Laboratory 13
A5.4 EPA 14
A5.5 Verification Test Stakeholders 14
A6 Background 15
A6.1 Technology Need 15
A6.2 Technology Description 17
A7 Verification Test Descrition and Schedule 18
A7.1 Verification Test Description 18
A7.2 Verification Schedule 19
A7.3 Test Facility 20
A8 Quality Objectives 20
A9 Special Training/Certification 21
A10 Documentation and Records 21
B MEASUREMENT AND DATA ACQUISITION 23
Bl Experimental Design 23
Bl.l Test Procedures 24
B 1.1.1 Laboratory Testing 24
Bl.1.2 Field Testing 27
Bl.l.2.1 Field Testing Procedures -Nitrate Sensor 29
Bl.l .2.2 Field Testing Procedures - Conventional
Groundwater Monitoring 29
Bl.l.3 Evaluation of Test Parameters 30
Bl.l.3.1 Accuracy 31
Bl.l.3.2 Variability of Readings 32
Bl.l.3.3 Duplication 32
Bl.l.3.4 Effect of Changes in Water Quality 33
Bl.l.3.5 Operational Factors 33
B1.2 Statistical Analysis 33
B 1.2.1 Accuracy 34
Bl.2.2 Variability of Readings 34
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B 1.2.3 Duplication 35
B 1.2.4 Effect of Changes in Water Quality 35
B1.3 Reporting 35
B2 Reference Sample Collection 36
B3 Sample Handling and Custody Requirements 36
B4 Reference Method 37
B5 Quality Control Requirements 37
B6 Instrument/Equipment Testing, Inspection, and Maintenance 38
B7 Instrument Calibration and Frequency 39
B8 Inspection/Acceptance of Supplies and Consumables 39
B9 Non-Direct Measurements 39
BIO Data Management 39
C ASSESSMENT AND OVERSIGHT 43
Cl Assessments and Response Actions 43
Cl.l Technical Systems Audits 43
C1.2 Performance Evaluation Audit 44
C1.3 Audit of Data Quality 44
C1.4 QA/QC Reporting 45
C2 Reports to Management 45
D DATA VALIDATION AND USABILITY 46
Dl Data Review, Validation, and Verification Requirements 46
D2 Validation and Verification Methods 46
D3 Reconciliation with User Requirements 46
E REFERENCES 47
Figures Page
Figure 1. Organization Chart for the Verification Test 10
Figure 2. Example ISE Sensors 18
Figure 3. Schematic Cross Section View of End of Tile Bioreactor at Kelly Farm,
Ames, IA 28
Tables Page
Table 1. Planned Verification Schedule 19
Table 2. Summary of Nitrate Sensor Laboratory Testing 26
Table 3. Summary of Nitrate Sensor Field Verification Monitoring using Conventional
Groundwater Monitoring Techniques 30
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Table 4. Summary of Nitrate Sensor Verification Samples 31
Table 5. Summary of Data Recording Process 31
Table 6. Summary of Reports to Management 43
Appendices Page
APPENDIX A: Conventional Groundwater Sampling Procedures 49
APPENDIX B: Field Activities Log 59
APPENDIX C: Field Sampling and Example Chain of Custody Forms 60
APPENDIX D: Nitrate Sensor Implementation Document 64
APPENDIX E: Laboratory Test Procedures 80
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A3 ACRONYMS AND ABBREVIATIONS
ADQ
AMS
ANOVA
ARS
bgs
DI
EPA
ETV
1C
ISE
LRB
MAE
MCL
MS/MSD
MSE
NELAC
NIST
NJDEP
NTU
OQA
PE
PVC
QA
QC
QCS
QMP
R2
RFIC
SRM
ISA
USDA
audit of data quality
Advanced Monitoring Systems
analysis-of-variance
Agricultural Research Service
below ground surface
deionized
U.S. Environmental Protection Agency
Environmental Technology Verification
ion chromatography
ion-selective electrode
laboratory record book
mean absolute error
maximum contaminant level
matrix spike/matrix spike duplicate
mean squared error
National Environmental Laboratory Accreditation Conference
National Institute of Standards and Technology
New Jersey Department of Environmental Protection
nephelometric turbidity unit
Office of Quality Assurance
performance evaluation
polyvinyl chloride
quality assurance
quality control
quality control sample
quality management plan
coefficient of determination
Reagent-Free Ion Chromatography
standard reference material
technical systems audit
United States Department of Agriculture
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A4 DISTRIBUTION LIST
Vendors
Gregg Gustafson
Instrumentation Northwest, Inc.
8902 122nd Ave. Northeast
Kirkland, WA 98033
EPA
Michael Brody
U.S. EPA/OCFO
Ariel Rios Building
1200 Pennsylvania Ave. NW, 2722A
Washington, DC 20460
John McKernan
Michelle Henderson
U.S. EPA
NRMRL/ORD/ETAV
26 W. Martin Luther King Dr., MS 208
Cincinnati, OH 45268
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Collaborators
Stuart Nagourney
New Jersey Department of Environmental
Protection
Office of Quality Assurance
9 Ewing Street
Trenton, NY 08625
Thomas Moorman
USDA/ARS
National Laboratory for Agriculture and the
Environment
Ames, Iowa 50010
Battelle
Amy Dindal
Andrew Barton
Nicole Albers
Zachary Willenberg
Battelle
505 King Avenue
Columbus, OH 43201
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A5 VERIFICATION TEST ORGANIZATION
The verification test will be conducted under the U.S. Environmental Protection Agency (EPA)
through the Environmental Technology Verification (ETV) Program. It will be performed by
Battelle, which is managing the ETV Advanced Monitoring Systems (AMS) Center through a
cooperative agreement with EPA. The scope of the AMS Center covers verification of
monitoring technologies for contaminants and natural species in air, water, and soil. This
verification will address sensors that provide real-time measurements of dissolved nitrate
concentrations in groundwater in support of remediation activities.
The day to day operations of this verification test will be coordinated and supervised by Battelle
personnel, with in-kind involvement from personnel of the United States Department of
Agriculture (USDA) Agricultural Research Service (ARS). Laboratory testing will be conducted
at the USDA ARS National Laboratory for Agriculture and the Environment in Ames, Iowa.
Field testing will be carried out by Battelle personnel and USDA ARS personnel under Battelle's
oversight at the test site in Ames, Iowa. The vendors will provide on-site assistance to Battelle
during the laboratory testing and during startup and commencement of field testing. The vendors
will provide Battelle and USDA personnel with instructions for use of their nitrate sensors and
enough nitrate sensors for implementation of field and laboratory testing.
The organization chart in Figure 1 identifies the responsibilities of the organizations and
individuals associated with the verification test. Roles and responsibilities are defined further
below. Quality assurance (QA) oversight will be provided by an auditor from the New Jersey
Department of Environmental Protection (NJDEP) Office of Quality Assurance (OQA) with
oversight from the Battelle Quality Manager and also by the EPA AMS Center Quality Manager,
at her discretion.
A5.1 Battelle
Andrew Barton is the AMS Center's Verification Test Coordinator for this test. In this role, Mr.
Barton will have overall responsibility for ensuring that the technical, schedule, and cost goals
established for the verification test are met. Specifically, Mr. Barton will:
• Prepare the draft test/QA plan, verification reports, and verification statements.
• Revise the draft test/QA plan, verification reports, and verification statements in
response to reviewers' comments.
• Assemble a team of qualified technical staff to conduct the verification test.
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Battelle
Management
Zachary Willenberg
Battelle AMS Center
Quality Manager
Amy Bowman
NJDEP
Quality Manager
USDAARS, National
Laboratory for
Agriculture and the
Environment
Amy Dindal
Battelle AMS
Center Manager
Andrew Barton
Battelle
Verification Test
Coordinator
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John McKernan
EPA AMS Center
Project Officer
Michelle Henderson
EPA AMS Center
Quality Manager
Nitrate Sensor
Vendors
Battelle
Technical Staff
Figure 1. Organization Chart for the Verification Test
Establish a budget for the verification test and manage staff to ensure the budget is
not exceeded.
Coordinate with the vendors for provision of nitrate sensors for testing.
Direct Battelle technical staff in the laboratory testing and coordinate with Battelle
and USD A ARS personnel for performance of the field testing.
Direct the team in performing the verification test in accordance with this test/QA
plan.
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• Hold a kick-off meeting approximately one week prior to the start of the verification
test to review the critical logistical, technical, and administrative aspects of the
verification test. Responsibility for each aspect of the verification test will be
confirmed.
• Ensure that all quality procedures specified in this EPA Quality Category III test/QA
plan and in the AMS Center Quality Management Plan1 (QMP) are followed.
• Serve as the primary point of contact for USDA ARS and vendor representatives.
• Ensure that confidentiality of sensitive vendor information is maintained.
• Assist vendors as needed during verification testing.
• Compile data from the first day of the verification test and provide the data to EPA
for review.
• Become familiar with the operation of the nitrate sensors through instruction by the
vendors, if needed.
• Prepare a deviation report for any departure from the test/QA plan during the
verification, obtain the requisite EPA and vendor approvals, and distribute the
approved report as specified in the AMS Center QMP.
• Respond to any issues raised in assessment reports, audits, or from test staff
observations, and institute corrective action as necessary.
• Coordinate review and distribution of the final test/QA plan, verification reports, and
verification statements.
Amy Dindal is Battelle's Manager for the AMS Center. As such, Ms. Dindal will oversee the
various stages of verification testing. Ms. Dindal will:
• Review the draft and final test/QA plan.
• Attend the verification test kick-off meeting.
• Review the draft and final verification reports and verification statements.
• Ensure that necessary Battelle resources, including staff and facilities, are committed
to the verification test.
• Maintain communication with EPA's technical and quality managers.
• Issue a stop work order if Battelle or EPA QA staff discover adverse findings that
will compromise test results.
Technical staff from Battelle will support Mr. Barton in planning and conducting the verification
test. The responsibilities of the technical staff will be to:
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• Assist in planning for the test, and making arrangements for the receipt of and
training on the nitrate sensors.
• Attend the verification test kick-off meeting.
• Conduct verification testing using the vendors' nitrate sensor technology.
• Perform statistical calculations specified in this test/QA plan on the technology data
as needed.
• Provide results of statistical calculations and associated discussion for the verification
reports as needed.
• Support Mr. Barton in responding to any issues raised in assessment reports and
audits related to statistics and data reduction as needed.
Zachary Willenberg is Battelle's Quality Manager for the AMS Center. Mr. Willenberg will:
• Review the draft and final test/QA plan.
• Attend the verification test kick-off meeting.
• Assist the NJDEP OQA auditor, as needed, in the conduct of the technical systems
audit (ISA) during the verification test. The ISA will address both the laboratory
and field components of nitrate sensor testing.
• Audit at least 10% of the verification data or designate other QA staff to conduct the
data audit.
• Prepare and distribute an assessment report for each audit.
• Verify implementation of any necessary corrective action.
• Request that Battelle's AMS Center Manager issue a stop work order if audits
indicate that data quality is being compromised.
• Provide a summary of the Q A/quality control (QC) activities and results for the
verification reports to Mr. Barton for review and submission to EPA in the final
verification test report.
• Review the draft and final verification reports and verification statements.
A5.2 Nitrate Sensor Vendors
The responsibilities of the nitrate sensor vendors are as follows:
• Review and provide comments on the draft test/QA plan.
• Perform an initial site visit to coordinate logistics for the field verification test.
• Initially install and program nitrate sensors at the start of the field verification test and
remove and field test (verify calibration) sensors at the end of the test.
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• Provide a minimum of four and a maximum of seven nitrate sensors for evaluation
during the verification test.
• Provide all other equipment/supplies/reagents/consumables needed to operate their
technology for the duration of the verification test.
• Provide on-site assistance with sensor implementation during the laboratory testing
and during startup and commencement of field testing.
• Supply training on the use of the technology, and provide written consent and
instructions for test staff to carry out verification testing, including written
instructions for routine operation of their technology.
• Perform/manage remote monitoring and dissemination of sensor data.
• Accept (by signature of a company representative) the final test/QA plan prior to test
initiation.
• Review and provide comments on the draft verification report and verification
statement for the nitrate sensor technology.
A5.3 USDA ARS National Laboratory for Agriculture and the Environment, Soil
Microbiology and Environmental Quality Laboratory
The primary point of contact for USDA ARS will be Thomas Moorman. Mr. Moorman will lead
USDA ARS personnel in meeting the following responsibilities for this verification:
• Provide laboratory space for the laboratory portion of the verification test.
• Provide access to and support at the field test site.
• Review and provide comments on the draft test/QA plan.
• Analyze all conventional groundwater field and associated QC samples for nitrate.
• Analyze conventional groundwater field and associated QC samples for nitrite as
nitrogen (nitrate-N) until negligible concentrations (i.e., <1 mg/L) are verified in
groundwater.
• Analyze all laboratory verification test and associated QC samples for nitrate.
• Provide sufficient personnel to collect weekly conventional groundwater samples at
the test site according to procedures outlined in this test/QA plan.
• Modify conditions at the test site (if necessary) to ensure parameter variability.
• Review and provide comments on the draft verification report and verification
statement for the nitrate sensor technologies.
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A5.4 EPA
EPA's responsibilities in the AMS Center are based on the requirements stated in the
"Environmental Technology Verification Program Quality Management Plan" (EPA ETV
QMP).2 The roles of specific EPA staff are as follows:
Michelle Henderson is EPA's AMS Center Quality Manager. For the verification test,
Ms. Henderson will:
• Review the draft and approve the final test/QA plan.
• Attend the verification kick-off meeting, as available.
• Review checklists, reports, report responses, and closure statements of TSA,
performance evaluation (PE) audits, and audits of data quality systems (ADQs)
conducted by NJDEP, and/or Battelle.
• Perform an external TSA of field and/or laboratory activities, PE audits, and/or an
audit of data quality during the verification test.
• Notify the EPA AMS Center Project Officer of the need for a stop work order if
evidence indicates that data quality is being compromised.
• Prepare and distribute an assessment report summarizing results of the external audit
performed.
• Review the first day of data from the verification test and provide immediate
comments if concerns are identified.
• Review the draft and approve the final verification reports and verification
statements.
John McKernan is EPA's Project Officer for the AMS Center. Dr. McKernan will:
• Review the draft test/QA plan.
• Approve the final test/QA plan.
• Attend the verification kick-off meeting, as available.
• Be available during the verification test to review and authorize any test/QA plan
deviations by phone and provide the name of a delegate to the Battelle AMS Center
Manager should he not be available during the testing period. Review the first day of
data from the verification test and provide immediate comments if concerns are
identified.
• Review the draft verification reports and verification statements.
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• Oversee the EPA review process for the test/QA plan, verification reports, and
verification statements.
• Coordinate the submission of verification reports and verification statements for final
EPA approval.
• Post the test QA plan, verification reports, and verification statements on the ETV
Web site.
A5.5 Verification Test Stakeholders
This test/QA plan and the verification report(s) and verification statement(s) based on testing
described in this document will be reviewed by experts in the fields related to nitrate sensor
technology. The following experts have been providing input to this test/QA plan and have
agreed to provide a peer review:
• Stu Nagourney, NJDEP (also AMS Center stakeholder)
• Amy Bowman, NJDEP (TSA auditor)
• Charles Spooner, EPA Office of Water
• Kenneth Wood, Dupont (also AMS Center stakeholder)
• Michael Brody, EPA Office of the Chief Financial Officer
The AMS Center Water Stakeholder Committee also was apprised of the status of verification
testing during periodic teleconferences and provided the opportunity to comment on the test
design before it was implemented into this test/QA plan.
A6 BACKGROUND
A6.1 Technology Need
The ETV Program's AMS Center conducts third-party performance testing of commercially
available technologies that detect or monitor natural species or contaminants in air, water, and
soil. The purpose of ETV is to provide objective and quality assured performance data on
environmental technologies, so that users, developers, regulators, and consultants can make
informed decisions about purchasing and applying these technologies. Stakeholder committees
of buyers and users of such technologies recommend technology categories, and technologies
within those categories, as priorities for testing. Verification reports from previous tests are
available at http://www.epa.gov/nrmrl/std/etv/verifiedtechnologies.html.
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As a result of human activity (i.e., transportation, industrial processes, and agriculture) the
annual transfer of nitrogen into biologically available forms has more than doubled.3
Throughout the 2006-2011 EPA Strategic Plan are strategic commitments and measures that
address emissions and concentrations of nitrogen and nitrogen compounds. This emphasis is
continued in the recently released public review draft of this Strategic Plan Change Document,
which can be found at http://www.epa.gov/cfo/plan/2006/entire_report.pdf. Based on the
increase in biologically available dissolved nitrate, coupled with the potentially toxic effects of
exposure at elevated concentrations, the EPA has set a maximum contaminant level (MCL) of
10 mg/L nitrate as nitrogen (nitrate-N) in drinking water.
Subsurface drainage from agricultural land commonly contains elevated dissolved nitrate
concentrations, and contributes a substantial portion of base flow in rivers in areas of North
America. In certain agricultural areas, drainage is promoted through the use of subsurface tiles
(drainage tubes), which typically are joined to larger drains or deliver water directly into small
streams. Concentrations of nitrate exiting subsurface tile drains frequently exceed 15 mg/L
(3.4 mg/L nitrate-N) in spring and early summer.4"9 This nitrogen export from Midwestern tile-
drained watersheds is a contributing factor to the hypoxia problem in the Gulf of Mexico.10 One
strategy for reducing nitrate concentrations in this agricultural drainage is an "end of tile
bioreactor", which is essentially an excavated cavity filled with wood chips. Tile drainage water
is commonly routed through this structure; the wood chips naturally support populations of
microorganisms that remove the nitrate through denitrification. Previous studies have shown
that bioreactors and denitrification walls reduce nitrate concentrations in drainage water in a
variety of settings.11"14
Underlying any approach to the reduction of nitrogen in the environment (i.e., groundwater) is
the need to measure concentrations in a timely and useful manner. Monitoring of environmental
contaminants in groundwater is currently a costly and often lengthy process that is accomplished
by collecting samples from wells using labor-intensive techniques, preserving and then shipping
the samples to an established laboratory where sample preparation, analysis and data reduction
are performed. This process is time consuming and may not yield data for days or even weeks
after sample collection, depending upon laboratory backlogs and report preparation timeframes.
This verification test will evaluate a newer approach to monitoring of groundwater in a
monitoring well, and in an end of tile bioreactor using environmental sensors. One of the
objectives is to compare conventional grab (or discrete) groundwater sampling results (which are
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often collected on a quarterly basis) to results collected on a continual basis using in situ sensors
to better design an optimal monitoring groundwater strategy that focuses on ensuring adequate
protection for human health and the environment.
A6.2 Technology Description
Environmental sensors are small, transportable analytical devices that provide data in real time,
are rugged enough to withstand a wide range of weather conditions, operate remotely, acquire
data continuously or on demand, and provide processed data directly to the user. Monitoring
costs could be reduced by the use of sensors placed directly in a well, thereby eliminating sample
collection and shipment costs, and reducing analytical costs and delays in data acquisition and
reporting. Sensors ideally can collect large amounts of data on a continuous basis over time,
with the sensor often placed in one location. Sensors can be used as a stand-alone to replace
current methods or to supplement current methods. Networked sensors also can provide many
more data points over a given time interval, thereby offering the potential to identify trends in
data and to observe less frequent but environmentally significant events that cannot currently be
observed by current sampling and analysis paradigms. The ETV verification described in this
test/QA plan will explore the effectiveness and ease of use of nitrate sensors and quantify their
response relative to conventional monitoring and laboratory analysis of dissolved nitrate in
groundwater.
A submersible nitrate sensor is capable of collecting in-situ measurements of dissolved nitrate
concentrations in groundwater. Although several types of nitrate sensors currently exist, this
verification test will focus on submersible sensors equipped with a nitrate-specific ion-selective
electrode (ISE) for monitoring dissolved nitrate concentrations. Nitrate-specific ISE sensors
typically work on the principal of direct potentiometry, whereby two electrodes (a sensing
electrode and a reference electrode) are contained within the sensor unit. The reference electrode
is immersed in a solution of a constant nitrate concentration within the sensor housing, and ionic
charge transfer between this solution and the sensing electrode is measured and converted to a
concentration that is representative of a dissolved nitrate concentration of the aqueous solution
being analyzed. Example ISE sensors are illustrated in Figure 2.
Submersible nitrate sensors are powered internally with alkaline batteries or with an auxiliary
power supply for data intensive applications. The sensor can be programmed to measure and
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collect data on a variety of time intervals, and can be connected to land-line modems that will
transmit real-time data for immediate download.
A7 VERIFICATION TEST DESCRIPTION AND SCHEDULE
A7.1 Verification Test Description
The purpose of this test/QA plan is to specify procedures for a verification test applicable to
commercial nitrate sensors. One aspect of the verification test is to compare dissolved nitrate
concentrations in groundwater measured by the deployed sensors to nitrate concentrations
collected using conventional groundwater monitoring techniques. In addition, a laboratory
verification test will be performed to evaluate the performance of the nitrate sensors in response
to simulated changes in field conditions. In performing the verification test, Battelle will follow
the technical and QA procedures specified in this test/QA plan and will comply with the data
quality requirements in the AMS Center QMP.1 This test/QA plan is an EPA QA Category III
evaluation.
C^e* E£
eusc-TO«
Figure 2. Example ISE Sensors
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A7.2 Verification Schedule
Table 1 shows the planned schedule of activities for the verification testing and data analysis and
reporting. Laboratory testing of the nitrate sensors will be initiated soon after final approval of
this test/QA plan; field sensor deployment and field verification testing will take place
simultaneously. As shown in Table 1, testing activities are planned to begin in the spring of
2010. Laboratory testing will commence first, and require approximately one week prior to field
deployment and verification testing. Field testing will require approximately two months to
complete. An ETV verification report will subsequently be drafted, and the report will be
reviewed simultaneously by the participating technology vendors, NJDEP, USD A, and EPA, and
subsequently by peer reviewers. The final reports will be submitted to EPA for final signature,
and the final reports will be made publicly available on the EPA/ETV Web site.
Table 1. Planned Verification Schedule
Month and Year
March 20 10
April 20 10
May-June 2010
June-July 20 10
August 20 10
September 20 10
Verification Activity
Testing
Prepare for laboratory
testing
Initiate and complete
laboratory testing
Initiate field testing
using sensors3
Perform field reference
sampling
Completion of field
testing of sensors
None
None
None
Data Analysis and Reporting
Begin preparation of ETV report template
Compile data from laboratory testing
Compile data from field verification testing
Review and summarize laboratory operator observations
Analyze laboratory test data
Analyze field test data
Review and summarize field operator observations
Analyze field test data
Prepare draft reports
Internal review of draft reports
Vendor/NJDEP/USD A/EPA review of draft reports
Revision of draft reports
Peer review of draft reports
Revision of draft reports
Submission of final reports for EPA approval
a: The start of field testing will be dependent upon weather conditions (i.e., whether groundwater is flowing in
the test cell and the recent occurrence of a precipitation event).
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A7.3 Test Facility
Laboratory analyses will be conducted in the USDA ARS laboratory in Ames, Iowa. In
performing this verification test, Battelle and the USDA ARS laboratory will follow the
procedures specified in this test/QA plan and will comply with quality requirements in the AMS
Center QMP.1 The USDA ARS laboratory that will be used is fully equipped for receiving,
documenting, preparing, and performing calibrated measurement of dissolved nitrate
concentrations in groundwater samples. The end of the tile bioreactor field site is located a few
miles from the USDA ARS laboratory in Ames.
A8 QUALITY OBJECTIVES
This verification test is designed to evaluate the performance of sensors for measuring dissolved
nitrate concentrations in groundwater. Laboratory verification testing will simulate field
monitoring of nitrate in groundwater and will include an evaluation of sensor performance in
accurately measuring nitrate concentrations in response to simulated variations in groundwater
field conditions (e.g., nitrite, turbidity, and chloride). Nitrate and the selected interference
parameters will be generated from stock solutions and injected at known concentrations to
challenge the sensors. Conventional samples will periodically be collected during the laboratory
testing and analyzed for verification of nitrate concentrations using ion chromatography (EPA
300.1). Field verification testing will consist of monitoring groundwater for nitrate using sensors
and a conventional groundwater sampling technique. The conventional groundwater samples
will be collected periodically during the field test and analyzed for verification of nitrate
concentrations using ion chromatography (EPA 300.1). In addition to analyzing for nitrate, the
groundwater samples will be analyzed for nitrite-N for one month or until negligible
concentrations (i.e., <1 mg/L) are verified in groundwater for two successive monitoring events.
The quality of the nitrate concentration data generated using the sensors will be documented by
calibration data, and documentation of the QA activities carried out at the field monitoring site.
For consistency and understanding of reported nitrate concentrations, it should be noted that the
nitrate sensors will be programmed to display and record concentrations as nitrate-N. The
laboratory ion chromatography (1C) procedure also was written based on evaluating and
reporting concentrations as nitrate-N. For comparison, 1 mg/L nitrate-N is equal to 4.4 mg/L
nitrate, so 3 mg/L nitrate (the lower reporting limit of the nitrate sensor) is 0.68 mg/L nitrate-N.
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QA/QC requirements will include a TSA, a PE audit, and an ADQ. The TSA will be conducted
by Ms. Amy Bowman, NJDEP OQA. The inclusion of the PE sample will be conducted by Mr.
Barton and the results of the PE audit will be reviewed by the Battelle Quality Manager who will
also conduct the ADQ. The planned audit procedures are described in Section Cl. The EPA
Quality Manager also may conduct an independent TSA, PE audit, and/or ADQ at her discretion.
A9 SPECIAL TRAINING/CERTIFICATION
The Battelle Quality Manager or NJDEP auditor may verify the presence of appropriate training
records prior to or during testing. Documentation of training related to technology testing, field
testing, laboratory testing, data analysis, and reporting is maintained for all Battelle technical
staff in training files at their respective locations. Battelle technical staff involved in this
verification will have experience in operation of sensor calibration and monitoring equipment.
In addition, the staff will have experience in operation and calibration of conventional
groundwater monitoring equipment, including inter-well decontamination procedures. All
Battelle and USD A personnel will receive on-site training by the vendor in the use of the nitrate
sensors selected for this verification test.
A10 DOCUMENTATION AND RECORDS
The records for this verification test will be contained in the test/QA plan, laboratory record
books (LRB), data collection forms, electronic files (both raw data and spreadsheets), the final
verification report, or assessment reports. Nitrate sensor field test data will be uploaded to an
internet (ftp) site that will be accessible with Windows®-based software. All of these records
will be maintained by the Verification Test Coordinator during the test and will be transferred to
permanent storage at Battelle's Records Management Office within two months of the
finalization of the verification reports. Electronic files containing field and laboratory results
will be disseminated to the project team on a bi-weekly basis. All Battelle LRBs are also stored
indefinitely, either by the Verification Test Coordinator or within two months of the finalization
of the verification reports in Battelle's Records Management Office. EPA will be notified before
disposal of any files. Section BIO further details the data recording practices and
responsibilities.
All written records will be in ink. Any corrections to notebook entries, or changes in recorded
data, will be made with a single line through the original entry. The correction is then to be
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entered, initialed, and dated by the person making the correction. In all cases, strict
confidentiality of data from the vendor's technology will be maintained.
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SECTION B
MEASUREMENT AND DATA ACQUISITION
Bl EXPERIMENTAL DESIGN
This test/QA plan addresses the verification of nitrate sensors through laboratory testing and
field monitoring of nitrate concentrations in groundwater. Specifically, nitrate sensors will be
evaluated for the following performance parameters:
• Accuracy
• Variability of readings
• Duplication of readings
• Effect of nitrite, turbidity, and chloride on nitrate sensor readings
• Operational factors including ease of use, downloading of data, timely dissemination
of data, and use of nitrate sensors for real-time remote data collection.
Sensor probes for other parameters (e.g., specific conductance, temperature, pH, groundwater
level, etc...) may be included with the nitrate sensor to better understand conditions within the
test cell. These data will be reviewed to determine whether potential interference parameters
may be affecting nitrate sensor readings. Prior to the deployment, critical interference parameter
levels, above or below which the sensors may be compromised, will be established by the vendor
using sensor technology criteria and water quality data from a groundwater sample collected
from the test cell. Should these critical levels be exceeded at any time during the verification
testing, nitrate sensor data will be immediately evaluated, the project team will be notified, the
level and duration of exceedance will be noted, and appropriate action (i.e., sensor recalibration)
will be taken. It should be noted that interference parameter sensor data will not be included in
the verification report; only nitrate sensor data will be evaluated and reported.
Accuracy will be determined by comparing nitrate sensor readings to reference nitrate
concentration measurements made in laboratory and field testing and analyzed in the laboratory
using EPA-approved analysis methods (EPA Method 300.1 for nitrate). Variability will be
assessed by observing the spread of nitrate sensor readings made at constant nitrate
concentrations (equated to drift) using stock solutions in the laboratory. Nitrate sensor
duplication of readings will be assessed by comparing nitrate sensor readings made by placing
duplicate nitrate sensors in a single test cell in the laboratory so they are exposed to identical
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concentrations simultaneously. The effect of nitrite, turbidity, and chloride on nitrate sensor
readings will be assessed in the laboratory by comparing nitrate sensor readings exposed at
constant nitrate concentrations but under varying degrees of nitrite, turbidity, and chloride.
Operator observations will be recorded in all laboratory and field testing to assess operational
factors of the nitrate sensors. Consistency of nitrate sensor readings over time will be assessed in
the accuracy of nitrate sensor readings made in the field and in the laboratory over time, verified
against laboratory analyses. The field testing evaluation (particularly the readings collected near
the end of the field study) will serve to evaluate the effects of sensor fouling on the accuracy and
duplication performance parameters.
Bl.l Test Procedures
The following sections describe the designed field and laboratory test procedures, and how these
test procedures will be used to evaluate each of the performance parameters listed above.
Bl.1.1 -Laboratory Testing
For laboratory testing, two test cells will be constructed using a 2-inch diameter, 4-foot high,
clear plastic (i.e., poly vinyl chloride [PVC]) pipe with a stopcock installed six inches above the
base. Two (2) bundled nitrate sensors will be deployed in the first test cell and one (1) sensor
will be deployed in the second test cell, each suspended at a depth where the base of the sensor is
six inches above the base of the test cell. The nitrate sensors will be calibrated prior to
deployment (see Section B7) and programmed to collect nitrate concentration measurements at
one minute intervals throughout the duration of the laboratory testing, which is expected to be
approximately 2 days.
Phase 1 of the laboratory testing will consist of filling a two-liter (2 L) graduated cylinder with a
mixture deionized (DI) water and an ionic strength adjuster exposed to air of normal
temperature. Use of an ionic strength adjuster (ammonium sulfate) will create uniform
background conditions in the test cells that will emulate field conditions, as natural waters have a
background ionic strength. This addition will normalize the activity of the ionic strength of the
solution and allow for sensor performance without the complication of calculating activity. The
solution will be spiked with known nitrate concentration prepared from a concentrated stock
solution to generate the desired nitrate concentration, using the following calculation to solve for
the desired volume of stock solution:
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Ci x Vi = C2 x V2
where: Ci = concentration of stock solution (mg/L)
Vi = volume of stock solution (L)
C2 = desired nitrate or interference parameter concentration (mg/L)
V2 = desired volume (L)
The solution in the graduated cylinder will be decanted into the two test cells (1 L per test cell)
and this process will be repeated for each desired nitrate concentration. The nitrate
concentrations will be randomly varied every 20 minutes, and will span the expected range of
nitrate concentrations observed in the field test cell (roughly 1 to 12 mg/L nitrate-N [3-53 mg/L
nitrate]) according to the schedule outlined in Table 2. Between each test, the test cell will be
drained with the stopcock and flushed with DI water, allowing time for the nitrate sensors to re-
equilibrate prior to spiking the test cells with subsequent nitrate solutions. A certified,
concentrated liquid stock solution of sodium or potassium nitrite will be purchased from a
laboratory supply company and appropriate volumes of the stock solution will be pipetted into
the graduated cylinder to achieve the desired concentrations. The concentration-specific order of
nitrate concentrations will be randomized to minimize the potential for error. It should be noted
that the nitrate levels may vary slightly (i.e., ±5%) from the desired level; however, the integrity
of the range in parameter levels, which is the objective of the laboratory testing, will still be
maintained.
Phase 2 of the laboratory testing will evaluate the effects of known interferences (e.g., changes in
nitrite, turbidity, and chloride) on the ability of the nitrate sensors to accurately measure nitrate
concentrations. The effects of each of these parameters will be evaluated separately by varying
the interference parameter within a specific range at varying nitrate concentrations (see Table 2).
The parameter- and concentration-specific order of interference parameter evaluation will be
randomized to minimize the potential for error. It should be noted that the interference
parameter levels may vary slightly (i.e., ±5%) from the desired level; however, the integrity of
the range in parameter levels, which is the objective of the laboratory interference parameter
testing, will still be maintained.
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Table 2. Summary of Nitrate Sensor Laboratory Testing
Phase
1
(^Mtrate
Only)
2
(^Mtrate rius
Interference)
Interference
Parameter
Chloride
Nitrite-N
Turbidity
Nitrate-N
Cone."
(mg/L)
1 (4.4)
3(13)
6(26)
12 (53)
1 (4.4)
3(13)
12 (53)
1 (4.4)
3 (13^
j \ij)
12 (53)
i //i /i\
1 (4.4)
3(13)
12 (53)
Interference
Parameter
Level
Chloride = ND
Temp. = ambient
Nitrite = ND
Turbidity = ND
100 mg/L
500 mg/L
2,500 mg/L
100 mg/L
500 mg/L
2,500 mg/L
100 mg/L
500 mg/L
2,500 mg/L
Img/L
2 mg/L
4 mg/L
Img/L
2 mg/L
4 mg/L
Img/L
2 mg/L
4 mg/L
1NTU
5NTU
1NTU
5NTU
1NTU
5NTU
Totals
Test
Duration"
(min)
20
20
20
20
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
320
No. of
Conventional
Samples
Collected per
Test Cell
28
Total No. of
Conventional
Samples0
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
56"
a: Duration indicates total time of test once nitrate and interference parameters have reached the desired levels;
actual duration per test may be longer.
b: Total number of samples does not include reference sampling QC samples (see Section B5). It is estimated that
approximately 15 reference QC samples will be collected in the laboratory verification test.
c: All samples will be analyzed for nitrate using EPA Method 300.1.
d: Equivalent nitrate concentrations in parentheses.
Note: The nitrate sensors will collect readings at one minute intervals throughout the entire laboratory test.
ND = non detect
NTU = nephelometric turbidity unit
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During Phase 2 of the laboratory test, stock solutions of varying nitrate, nitrite, turbidity, and
chloride concentrations will be generated in a manner similar to that described above. Certified,
concentrated stock solutions of potassium nitrite (or similar), sodium chloride (or similar), and
formazin (or similar for turbidity) will be purchased from a laboratory supply company and
appropriate volumes of the stock solution will be pipetted into the graduated cylinder and
subsequently into the test cells to achieve the desired concentrations. The interference parameter
concentrations will be randomly varied every 10 minutes according to the schedule outlined in
Table 2.
During laboratory testing, water samples will be collected from the test cells for laboratory
analysis of nitrate concentrations using EPA Method 300.1. The laboratory analyses will be used
to monitor changes in nitrate concentrations during the test, and will be compared to data
collected using the nitrate sensors. The sampling frequency for the laboratory analyses is
summarized in Table 2, with one conventional sample being collected for each nitrate
concentration during Phase 1, and each interference parameter variation during Phase 2. Water
samples will be collected from a stopcock installed in the plastic piping at a depth consistent with
the sensor electrode. Water samples will then be collected by filling two 125 mL poly containers
from discharge tubing attached to the stopcock. The water samples will be labeled and
temporarily stored on site in a cooler at 4°C prior to same-day delivery to the USDA laboratory
for analysis. The laboratory will receive, process, analyze, and report results within 48 hours of
sample collection. The procedure for collecting water samples and for sample preparation and
shipment is included as Appendix A. Example field activities log sheets and field sampling logs
are provided in Appendices B and C, respectively.
Bl.1.2 - Field Testing
Field testing will consist of nitrate sensor deployment to monitor dissolved nitrate concentrations
within an end of tile bioreactor located at the Kelly Farm research site in Ames, IA. A cross-
section schematic of the site is shown in Figure 3, and illustrates the location of the inlet and
outlet pipelines, and the three monitoring wells that are screened from 2 to 6 ft below ground
surface (bgs). Reference sampling also will be performed using conventional groundwater
monitoring techniques. The following subsections discuss the field testing components in more
detail.
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End of Drainage Tile Bioreactor- Kelly Farm, Ames Iowa
Chip trench box 2 X 4 X 24
3 - 2" wells
9 thermocouples at 3 depths in wood chi
2 - 4" chip accesses
S" open pipe, slotted bottoi
6 mil Duraliner sheets X 2
6 gas suction lines
Figure 3. Schematic Cross Section View of End of Tile Bioreactor at Kelly Farm, Ames, IA
It should be noted that the quality and objectivity of the field evaluations conducted by USD A
and Battelle will be assured by the efforts of Battelle technical and NJDEP QAO staff. The
Battelle Verification Test Coordinator (Mr. Barton) will communicate the procedures and
expectations for nitrate sensor evaluation to both the USDA and sensor vendor representatives by
verbal and written means including this test/QA plan. That communication will be maintained
before, during, and after the periods of field testing, and will continue in the data analysis phase
of the verification.
Prior to field testing, a groundwater sample will be collected from one of the monitoring wells in
the test cell and analyzed by the USDA laboratory for nitrate, the interference parameters
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evaluated in the laboratory (nitrite, chloride, and turbidity), and other potentially interfering
parameters such as bromide and sulfate. Information from these analyses will assist in
programming the nitrate sensor prior to field deployment, and in evaluating the quality of the
nitrate sensor data.
Bl. 1.2.1 - Field Testing Procedures - Nitrate Sensor
Nitrate sensors will be deployed to monitor dissolved nitrate concentrations at the bioreactor in
the three 2-inch monitoring wells (Well #1, Well #2, and Well #3) and in the inlet sump. A
nitrate sensor will be deployed in Well #1 and in Well #3 at a midpoint depth of 4 ft bgs. In
Well #2, two nitrate sensors will be deployed at depths of 3 and 5 ft bgs to evaluate the existence
of vertical gradients within the test cell. A nitrate sensor also will be deployed in the inlet sump
approximately 90 ft upgradient of the upgradient edge of the bioreactor. Once the nitrate
sensors have been calibrated (see Section B7), they will be deployed in the well for a period of
two months and programmed to collect nitrate concentration measurements at a frequency of 15
minutes. Additional sensor testing/calibration will be performed once the nitrate sensors have
been removed from the well at the end of the field test. The sensors will be equipped with
wireless transmitters attached to the sensor cable that will be located at the top of the well casing
and will transmit real-time data to a laptop located in a building on the Iowa State University
Swine Nutrition Farm campus located approximately 300 yards to the southeast of the bioreactor.
The data will be uploaded to the laptop and transmitted to a password protected Internet site
using existing phone lines for immediate download by the project team.
Bl.1.2.2 —Field Testing Procedures — Conventional Groundwater Monitoring
Concurrent with the nitrate sensor deployment within the bioreactor, field verification testing
will be performed consisting of collecting groundwater samples, groundwater-level elevations,
and inlet flow rates. Inlet flow rates will be measured in the inlet pipeline by USDA personnel
using an in-line flow meter. Groundwater-level elevation data will be collected using a
measuring tape/sounder that is lowered into the monitoring well until the depth to groundwater is
reached and recorded. The conventional groundwater sampling technique will consist of sample
collection using a peristaltic pump and dedicated Teflon® tubing. The dedicated tubing will be
installed in the well so that the inlet is located at the same depth as the sensor electrode, and the
open end at the surface will be capped to minimize fouling within the tubing. When collecting
samples, the cap will be removed, the tubing will be attached to the peristaltic pump and the
pump will be operated at the lowest allowable setting to extract groundwater from the well. One
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to two pore volumes (within the Teflon® tubing) will be extracted from the well prior to sample
collection; the volume of water will be calculated using the inner radius of the tubing and the
thickness of the water column (inlet depth minus depth to groundwater). Groundwater samples
will then be collected by filling two 125 mL poly containers from the discharge tubing. The
groundwater samples will be labeled and temporarily stored on site in a cooler at 4°C prior to
delivery to the USDA laboratory for analysis. The laboratory will receive, process, analyze, and
report results within 48 hours of sample collection. The procedure for collecting groundwater-
level elevations and groundwater samples, and for sample preparation and shipment, is included
as Appendix A. Example field activities log sheets and field sampling logs are provided in
Appendices B and C, respectively.
The field reference monitoring schedule is presented in Table 3. Throughout the 2-month sensor
deployment, groundwater monitoring (including collection of groundwater-level elevations,
groundwater samples, and inlet flow rates) will be performed at each of the five monitoring
locations on a weekly basis to simulate a more conventional groundwater monitoring approach.
For two days at the beginning and two days at the end of the nitrate sensor deployment, more
intensive hourly monitoring of the aforementioned parameters will be performed. The intensive
monitoring at the beginning of the deployment is designed to provide initial verification of the
sensor monitoring, whereas the intensive monitoring at the end of the test is designed to verify
the accuracy of the unit after a significant deployment period where sensor biofouling within the
well may be an issue. An attempt will be made to perform these intensive two-day sampling
efforts immediately after a rainfall event to maximize the variation in nitrate concentrations in
the bioreactor that is expected after such an event due to increased subsurface drainage routed
through the inlet.
During field verification monitoring, approximately 252 groundwater and associated QA/QC
samples will be collected for analysis of nitrate concentrations. It is anticipated that 64 samples
will be analyzed during the weekly sampling and 94 samples during each of the 2-day intensive
sampling events at the beginning and end of field testing (see Table 3). The number of QA/QC
samples may vary based on unforeseen factors encountered during the field testing. It should be
noted that the samples also will be analyzed for nitrite for one month or until negligible
concentrations (i.e., <1 mg/L nitrite-N) are verified in groundwater for two successive
monitoring events.
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Table 3. Summary of Nitrate Sensor Field Verification Monitoring using Conventional
Groundwater Monitoring Techniques
Sample
Frequency
Weekly
Hourly
Hourly
Duration
2 months
2 days
(beginning of deployment)
2 days
(end of deployment)
Anticipated
Number of Field
Samples
40
80
80
Associated QC
Samples"
24
14
14
Total Number of
Samples
64
94
94
a: Estimated number of QC samples (see Section B5).
Bl. 1.3 - Evaluation of Test Parameters
Table 4 summarizes the types and numbers of samples that will be used to verify performance of
each nitrate sensor. A summary of the sampling requirements in regard to the test performance
parameters identified in Section Bl is presented in the following subsections.
Table 4. Summary of Nitrate Sensor Verification Samples
Sample Type
Phase 1 laboratory
water samples
Phase 2 laboratory
water samples
Field groundwater
samples
User observations
Responsible
Organization
Battelle
Battelle
Battelle/USDA
Battelle/USDA
Approximate
Number of Samples
or Readings
80
240
200
As needed
Associated QC
Samples
Equipment rinsates
"Field" duplicates
Laboratory QA/QC
Equipment rinsates
"Field" duplicates
Laboratory QA/QC
Equipment rinsates
Field duplicates
Laboratory QA/QC
NA
Uses
Accuracy, variability,
duplication, user
agreement.
Accuracy,
duplication, effect of
changes in water
quality, user
agreement.
Accuracy, effect of
changes in water
quality, user
agreement
Operational factors
Bl. 1.3.1 — Accuracy
Prior to deployment and testing, each nitrate sensor will be calibrated by the vendor; an example
calibration procedure is presented in Appendix D. Immediately after calibration, the sensor will
be programmed to take a few readings while the sensor is still in the reference standard(s) to
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verify the accuracy of the initial calibration. The accuracy of the nitrate sensor in the field and in
the laboratory will be determined by comparing nitrate sensor readings to simultaneous
measurements made using conventional groundwater sampling techniques. The comparison of
accuracy will be made statistically and graphically, by plotting nitrate sensor readings
(concentrations) against the nitrate concentrations measured in groundwater samples collected
using conventional techniques.
In the laboratory testing (as described in Section B1.1.1 and summarized in Table 2), nitrate
concentrations will be generated from a concentrated stock solution. In Phase 1 of the laboratory
testing, four nitrate concentrations (1, 3, 6, and 12 mg/L nitrate-N, or 4.4, 13, 26, and 53 mg/L
nitrate), spanning the range of anticipated field concentrations, will be generated and evaluated
with the nitrate sensors and conventional groundwater samples. In addition, concentrations of
interference parameters will be introduced into the laboratory test cells in Phase 2 of the
laboratory test to evaluate the ability of the nitrate sensor to accurately measure nitrate
concentrations under a variety of hypothetical field conditions.
E.l.1.3.2 — Variability of Readings
Variability of nitrate sensor concentration readings refers to the consistency, or lack thereof, in
reported nitrate concentrations with a constant nitrate concentration. Variability will be assessed
in Phase 1 of the laboratory evaluation using the multiple readings (20) made by each of three
sensors deployed in separate test cells at four reference nitrate concentrations (1, 3, 6, and
12 mg/L nitrate-N), as described in Section B1.1.1. Variability will be equated to drift and
expressed as percentage change in concentration as a function of time compared to the reference
concentrations.
Bl.1.3.3 - Duplication
The degree of agreement of nitrate concentrations reported simultaneously using duplicate nitrate
sensors will be assessed in the laboratory in the two test cells. As discussed in Section B 1.1.1,
the first test cell will house two nitrate sensors to evaluate intra-well duplication within the test
cell, whereas the second test cell will house one nitrate sensor to evaluate inter-well duplication
between the two test cells. The three nitrate sensors will be synchronized and programmed to
record nitrate concentrations at one minute intervals throughout Phase 1 and Phase 2 of the
laboratory test to allow direct comparison of nitrate concentration data.
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B.l.1.3.4 -Effect of Changes in Water Quality
The effect of water quality (i.e., interference parameters) on nitrate sensor response to nitrate
concentrations will be evaluated in Phase 1 and Phase 2 of the laboratory testing by exposing
nitrate sensors to constant nitrate concentrations under different water quality conditions. The
proposed laboratory testing schedule is described in Section B1.1.1 and summarized in Table 2.
In Phase 1 of the laboratory test, nitrate concentration readings under ambient water quality
conditions will be evaluated to formulate a baseline for comparison to the effects of changes in
water quality due to the introduction of interference parameters (e.g., varying concentrations of
nitrate, chloride, and turbidity). In Phase 2 of the laboratory test, three different constant nitrate
concentrations will be used (1, 3, and 12 mg/L nitrate-N), spanning the range of suspected field
concentrations. For each nitrate concentration, water quality will be modified as follows:
chloride will be spiked at 100, 500, and 2,500 mg/L; nitrite will be spiked at 1, 2, and 4 mg/L
nitrate-N; and turbidity will be spiked at 1 and 5 NTU. The ability of the nitrate sensors to
accurately measure nitrate concentrations will be evaluated under each of these 24 different
scenarios.
El. 1.3.5 — Operational Factors
Operational factors associated with use of the nitrate sensors will be evaluated based on the
comments and observations of all users (Battelle and USD A) in the laboratory and field testing.
Such observations may address the convenience of the nitrate sensors, the completeness of
nitrate sensor readings (percent data collected), their reliability under differing conditions, the
apparent consistency of nitrate sensor readings, and acceptability as a groundwater monitoring
tool. Observations also will include any noted biofouling during (if sensors are to be inspected
periodically) and at the end of the field testing period. In addition, data dissemination also will
be evaluated, such as ease of data transmission, timeliness of data dissemination, ease of data
downloading, and usability of downloaded data. In particular the observations of Battelle and
USDA users will be important, as those users are likely to be the relatively non-technically
trained users for which the nitrate sensors are designed. Cost for the nitrate sensor and
associated data transmission equipment also will be reported.
B1.2 Statistical Analysis
Statistical comparisons will be made between nitrate concentrations measured using the nitrate
sensor and those measured in the laboratory using EPA Method 300.1 from analysis of samples
collected using the conventional groundwater sampling technique. It is assumed that the nitrate
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concentration value represents the actual or target nitrate concentration present in the well
against which the nitrate sensor concentration will be evaluated. The planned statistical
comparisons are described in the following subsections.
B. 1.2.1 — Accuracy
The accuracy of the nitrate sensor concentrations with respect to the laboratory measured
concentrations will be assessed graphically and by evaluating the differences between paired
concentrations (concentration residuals) from measurements collected simultaneously at the
same location. The nitrate sensor concentration reading collected closest in time associated with
the collection of the conventional monitoring sample will be used for paired comparison. Two
statistical measurements will be used to assess the accuracy: (1) inference about the mean
difference, and (2) estimation of the mean absolute error (MAE). The inference about the
observed difference will include estimation of the mean difference and a statistical hypothesis
about whether the mean difference is equal to or different from zero (using either a paired-
sample t-test or a nonparametric equivalent). If the hypothesis test determines that there is a
difference in two measurement methods, the estimated average difference will be used as an
estimate of the bias for the nitrate sensors. The MAE will be calculated for the concentration
differences as follows:
n
1 V
MAE = — > [laboratory concentration, — nitrate sensor concentration, |
where n is the number of paired nitrate concentration measurements. The MAE will be used to
represent the average absolute difference in the two measurement methods.
The accuracy estimates will be calculated separately for Phase 1 and Phase 2 of the laboratory
evaluation and for the field evaluation. In addition, comprehensive accuracy estimates will be
calculated using all of the paired data sets from the field and laboratory evaluation.
Bl.2.2 - Variability of Readings
Variability of the nitrate sensor concentration readings will be evaluated using data from Phase 1
of the laboratory evaluation using the multiple readings (20) made by each of three sensors
deployed in separate test cells at four reference nitrate concentrations (1, 3, 6, and 12 mg/L
nitrate-N). Variability will be expressed as the standard deviation of the sensor concentration
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readings calculated two ways: (1) using the reference concentrations as the average (mean)
values for comparison, and (2) using the measured mean concentrations from the samples.
Standard deviation values will be calculated for each of the four reference concentrations.
Bl.2.3 -Duplication
The degree of agreement of nitrate concentrations reported simultaneously using duplicate nitrate
sensors will be assessed in the laboratory evaluation. The first test cell will house two nitrate
sensors to evaluate intra-well duplication within the test cell, whereas the second test cell will
house one nitrate sensor to evaluate inter-well duplication between the two test cells. The degree
of agreement between each pair of reported nitrate concentrations (inter-well and intra-well) will
be assessed by calculating the intra-well mean square error (MSB) and inter-well MSB using a
random-effects analysis-of-variance (ANOVA) model.
Bl.2.4 — Effect of Changes in Water Quality
The effect of changes in water quality on nitrate sensor performance will be assessed using the
data from Phase 2 of the laboratory evaluation (see Section B 1.1.1) by calculating the accuracy,
variability, and nitrate sensor duplication of readings (Sections Bl.2.1 through Bl.2.3) of the test
data at each of the water quality conditions outlined in Table 2. Those results will be compared
to indicate whether changes in nitrate, turbidity, and chloride concentrations have any apparent
effect on the nitrate sensor performance at constant nitrate concentrations. Accuracy or
variability results that differ by more than 5% or nitrate sensor duplication results that differ by
more than 20% will be taken as evidence of a significant water quality effect, and will be
thoroughly documented in the verification report.
B1.3 Reporting
The statistical comparisons described above will be conducted for the nitrate concentrations
collected in the field and/or laboratory using the nitrate sensor and conventional groundwater
monitoring, and user comments on the operational factors will be compiled and reported. A
verification report will be prepared for the nitrate sensor that presents the test procedures and test
data, as well as the results of the statistical evaluation of those data.
Operational aspects of the nitrate sensors will be recorded by testing staff at the time of use, and
summarized in the verification report. The verification report will briefly describe the ETV
program, the AMS Center, the test equipment and test conditions, and the procedures used in
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verification testing. The results of the verification test will be stated quantitatively, without
comment on the acceptability of the technology's performance. The draft verification report will
first be subjected to review by the technology vendor, USD A, and NJDEP, and then revised and
subjected to a review by EPA and/or other peer reviewers. The EPA comments and the peer
review comments will be addressed in further revisions of the report, and the comments and
responses will be tabulated to document the peer review process. The reporting and review
process will be conducted according to the requirements of the AMS Center QMP.1
B2 REFERENCE SAMPLE COLLECTION
Reference sample collection in this verification test consists of laboratory analysis of water
samples collected using a peristaltic pump in the laboratory test (see Section B 1.1.1), and
groundwater samples collected using a peristaltic pump during the field verification test (see
Section B1.1.2.2 and Appendix A). These reference samples will then be compared with the
corresponding readings collected concurrently with the nitrate sensors. In addition, the nitrate
sensors will be calibrated against reference solutions prior to deployment in the laboratory and in
the field as described in Section B7 and documented in Appendix D. The procedures and
records of reference method calibrations will be reviewed for both laboratory and field testing as
part of the TSA (Section Cl.l).
B3 SAMPLE HANDLING AND CUSTODY REQUIREMENTS
For all samples collected by means of conventional groundwater sampling methods during the
verification test, sample custody will be documented throughout collection, transport, shipping
(if necessary), and analysis of the samples on standard forms used by the USDA ARS National
Laboratory or forms provided by Battelle. Field activity logs (Appendix B), field sampling form
data sheets (Appendix C), and sample custody forms (Appendix C) will be filled in by USDA
and Battelle representatives. USDA ARS National Laboratory representatives conducting the
laboratory portion will document sample custody from collection to analysis using the field
sampling form data sheets (Appendix C). Copies of all data sheets will be retained by the
respective organization that conducted the sampling and analysis, and the originals will be sent
to Battelle by tracked shipment (FedEx or similar) for compilation of the data.
Real-time data collected with the nitrate sensors will be transmitted to a laptop located on the
Iowa State University campus. The laptop will transmit the data to a password protected Internet
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site via phone lines where it will be downloaded by the project team. All field data captured by
the sensors, including any calibrations performed in the field, will be exported to a usable format
and sent to Battelle by tracked shipment for compilation of the data.
B4 REFERENCE METHOD
All conventional groundwater samples collected will be analyzed following the laboratory
reference method, "Determination of Inorganic Anions by Ion Chromatography" (EPA Method
300.1) for determination of nitrate in the collected groundwater. Samples will be collected with
adequate volume (125 mL) in glass or plastic containers that have been rinsed with DI water,
preserved by refrigeration to 4°C ± 2°C and analyzed within 48 hours of collection. The
collection of the samples will be the responsibility of USD A and Battelle staff. In laboratory
analysis a Dionex ICS-2000 Reagent-Free Ion Chromatography (RFIC) System will be operated
by USD A National Laboratory staff according to instrument procedures (Appendix E) and the
manufacturers' instructions, including those for warm-up and stabilization time before testing.
The USDA Laboratory is responsible for coordinating the analysis of the samples with
associated QA/QC. Calibration and maintenance documentation for the Dionex ICS-2000, and
all results of the reference analyses will be provided to Battelle. A laboratory audit will be
performed by the NJDEP according to guidelines provided by the National Environmental
Laboratory Accreditation Conference (NELAC) Institute.
B5 QUALITY CONTROL REQUIREMENTS
Steps will be taken to maintain the quality of data collected during this verification test. The
reference laboratory will follow their standard QA/QC protocols for analysis of quality control
samples (QCSs) with each set of samples analyzed. QCSs producing results not meeting the
laboratory's standard requirements will be reanalyzed. If the results are still outside the required
tolerance, the reference instrument will be recalibrated and the samples reanalyzed. If the
outlying results persist, the affected data will be flagged and a repeat of the affected parts of the
verification test may be considered. Sample results not meeting these requirements will be
flagged and excluded from comparison to the nitrate sensor results.
During groundwater sampling activities, QC samples, including field duplicates, matrix
spike/matrix spike duplicates (MS/MSD), and equipment blanks, will be collected to ensure the
reliability of data. Duplicate groundwater samples will be collected at a frequency of one for
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every 10 samples (i.e., 10%) to evaluate the reproducibility of analytical results. MS/MSD
samples are used by the laboratory to evaluate the accuracy of its methods and equipment, and
will be collected at a frequency of one for every 20 samples (i.e., 5%). Equipment blanks, also
referred to as rinsate blanks, are collected to evaluate the potential for sample cross-
contamination from the sampling equipment used. Equipment rinsate blanks will be collected
daily, during sampling, for the groundwater sampling equipment to ensure that nondedicated
sampling devices have been decontaminated effectively. A complete description of groundwater
sampling QC samples is provided in Appendix A.
Quality of the laboratory reference nitrate (and nitrite) measurements will be ensured by a
calibration of the Dionex ICS-2000 RFIC before any testing. A pre-testing calibration curve is
prepared for each analytical run; the curve is expected to be linear with the coefficient of
determination (R2) greater than or equal to 0.995 before proceeding with analysis. Calibration is
verified throughout the analytical run by inserting calibration check standards and reagent blanks
with every set of 10 samples. The calibration and all verifications are incorporated into the run
alongside the samples and visually evaluated by the instrument operator to meet the reference
laboratory's QC criteria. The results of the analytical runs are copied into Microsoft® Excel files
and the original files are retained at the laboratory work station. A complete description of the
USDA National Laboratory's current Dionex ICS-2000 RFIC analytical procedures including
equipment, standards, reagents, and calibration is included in Appendix E. Standard reference
materials (SRMs) from the National Institute for Standards and Technology (NIST) shall be
included as part of the regime to ensure laboratory testing. A minimum of 10% of samples shall
be NIST SRMs with concentrations within the operational or working range of the test regime.
B6 INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE
The nitrate sensors used in the verification test will be tested, inspected, maintained, and
calibrated prior to deployment by the technology vendor according to manufacturer
specifications so as to meet the QC requirements stated in Section B5. Sample documentation
for implementation of a nitrate sensor is included as Appendix D. The Dionex ICS-2000 system
used to perform the laboratory nitrate analysis also will be tested, inspected, maintained, and
calibrated so as to meet the QC requirements stated in Section B5. The Dionex ICS-2000 system
analytical procedures are included as Appendix E. Other equipment, such as the water-level and
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flow monitoring instruments, will be obtained from the Battelle Instrument Services Laboratory
or the USDA laboratory and will have been inspected and calibrated within the past year.
B7 INSTRUMENT CALIBRATION AND FREQUENCY
The nitrate sensors will initially be calibrated prior to the laboratory test, and recalibrated
between the laboratory and the field evaluation by the vendor (see Appendix D). No calibration
verification is anticipated for the nitrate sensors during the evaluation; however, if calibration
becomes necessary, the vendor will be consulted and the procedure will be thoroughly
documented.
The instrumentation used by the reference laboratory for the reference analyses will be calibrated
per the USDA procedures (Appendix E). Documentation of the instrument calibration, standard
solutions and maintenance will be provided to Battelle. Other instrumentation used in this
verification test, such as a multi-parameter water probe and balances, will have been calibrated
within the 12 months prior to this verification test and documentation of the calibration provided
to Battelle. If possible, the calibration will be verified immediately prior to use in this
verification test.
B8 INSPECTION/ACCEPTANCE OF SUPPLIES AND CONSUMABLES
All materials, supplies, and consumables will be ordered by the Verification Test Coordinator or
designee. Where possible, Battelle will rely on sources of materials and consumables that have
been used previously as part of ETV verification testing without problems.
B9 NON-DIRECT MEASUREMENTS
Data published previously in the scientific literature will not be used to evaluate the vendor's
technology during this verification test.
BIO DATA MANAGEMENT
Various types of data will be acquired and recorded electronically or manually by Battelle,
USDA, and the technology vendor during this verification test. Table 5 summarizes the types of
data to be recorded, how and by whom the data will be recorded, and how the data will be treated
or used. Preprinted data sheets (Appendix B and C) will be used by USDA or Battelle staff to
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Table 5. Summary of Data Recording Process
Data to Be Recorded
Conventional field
groundwater sampling
data - groundwater-
level elevations, purge
volume, sample
collection, inlet flow
rates and field
observations
Laboratory nitrate
analyses data
Laboratory nitrite
analyses data
Laboratory QA results
Nitrate sensor readings -
field
Sensor readings of
temperature, water
level, specific
conductance
Nitrate sensor readings
- laboratory test cell
data
Conventional sampling -
laboratory
Laboratory conventional
sampling QA results
Where Recorded
Field activities log
(Appendix B)
Field sampling form
(Appendix C)
Laboratory data sheets or
recorded electronically by
USDA
Laboratory data sheets or
recorded electronically by
USDA
Laboratory data sheets or
recorded electronically by
USDA
Data uploaded to laptop
Data uploaded to laptop
Data uploaded to laptop
Laboratory data sheets or
recorded electronically by
USDA
Laboratory data sheets or
recorded electronically by
USDA
How Often Recorded
Weekly for duration of
field verification test (2
months); hourly for 2
days at beginning and 2
days at end of field test -
each sampling event
Each analysis
Each analysis (if above 1
mg/L for consecutive
events)
Each analysis
Every 15 minutes for 2
months
Every 15 minutes for 2
months
Every 15 minutes for
duration of test (~2 days)
Periodically according to
schedule in Table 2
Coincide with laboratory
conventional sampling
Disposition of Data
Incorporated in verification
report as necessary
Converted to spreadsheet for
statistical analysis and
comparisons
Converted to spreadsheet for
statistical analysis and
comparisons (if above 1
mg/L for consecutive events)
Incorporated in verification
report as necessary
Converted to spreadsheet for
statistical analysis and
comparisons
Data retained but not to be
used in comparative analysis
for this verification
Converted to spreadsheets for
statistical analysis and
comparisons
Converted to spreadsheets for
statistical analysis and
comparisons
Incorporated in verification
report as necessary
record sampling activities and observations in the field. All observations relevant to the
laboratory testing of the nitrate sensor will be documented by USDA laboratory staff either
electronically or in LRBs. Monitoring data from the field sensors will be transmitted in
electronic format and made usable by windows-based software. If possible, it will be requested
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that the files be provided to Battelle. The secondary probes connected to the nitrate sensor will
be collecting data that will be recorded (such as water level and specific conductance); however,
these readings will be supplementary and will not be verified in this evaluation.
All appropriate Battelle and USDA LRBs, record books and files will be forwarded (if
necessary) to Battelle for permanent storage, either by the Verification Test Coordinator or
Battelle's Records Management Office. EPA will be notified before disposal of any files.
Battelle will provide technology test data and associated reference data (including records; data
sheets; notebook records) from the first day of testing within one day of receipt to EPA for
simultaneous review. The goal of this data delivery schedule is prompt identification and
resolution of any data collection or recording issues. During the two-month field deployment,
reference data from USDA will be sent on a weekly basis to the Battelle Verification Test
Coordinator. Sensor data will be immediately available via an ftp site to the entire project team.
Records generated by any Battelle staff during the verification test will be reviewed by a Battelle
staff member within two weeks of generation, before the records are used to calculate, evaluate,
or report verification results. This review will be performed by a Battelle technical staff member
involved in the verification test, but not the staff member who originally received or generated
the record. The review will be documented by the person performing the review by adding
his/her initials and date to the hard copy of the record being reviewed. Data entered from hard
copy records into spreadsheets will be reviewed in hard copy within the two-week window.
Spreadsheet entries will be checked as part of the ADQ (Section C1.3). In addition, any
calculations performed by Battelle staff will be spot-checked by another Battelle technical staff
member to ensure that calculations are performed correctly.
Field data sheets filled out by USDA, the technology vendor, or Battelle representatives will be
reviewed by the lead USDA, technology vendor, or Battelle representative for completeness and
consistency within one week after they are filled out. USDA will then retain copies of their
respective data sheets and send the originals to Battelle. The Battelle Verification Test
Coordinator will review all such data sheets immediately upon receipt. Any corrections needed
in the forms will be implemented immediately, with consultation with the Battelle Quality
Manager, as needed.
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In addition to the Battelle Verification Test Coordinator performing a 100% data review and
EPA's review of the first day's data, an audit of data quality will be conducted. This audit will
consist of a review by the Battelle Quality Manager of at least 10% of the test data. During the
course of any such audit, the Battelle Quality Manager will inform the technical staff of any
findings and any immediate corrective action that should be taken. If serious data quality
problems exist, the Battelle Quality Manager will notify the AMS Center Manager, who is
authorized to stop work. Once the assessment report has been prepared, the Verification Test
Coordinator will ensure that a response is provided for each adverse finding or potential
problem, and will implement any necessary follow-up corrective action. The Battelle Quality
Manager will ensure that follow-up corrective action has been taken.
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SECTION C
ASSESSMENT AND OVERSIGHT
Cl ASSESSMENTS AND RESPONSE ACTIONS
Every effort will be made in this verification test to anticipate and resolve potential problems
before the quality of performance is compromised. One of the major objectives of this test/QA
plan is to establish mechanisms necessary to ensure this. The procedures described in this
test/QA plan, which is peer reviewed by a panel of outside experts, implemented by the technical
staff and monitored by the Verification Test Coordinator, will give information on data quality
on a day-to-day basis. The responsibility for interpreting the results of these checks and
resolving any potential problems resides with the Verification Test Coordinator. Technical staff
has the responsibility to identify problems that could affect data quality or the ability to use the
data. Any problems that are identified will be reported to the Verification Test Coordinator, who
will work with the Battelle Quality Manager to resolve any issues. Action will be taken to
control the problem, identify a solution to the problem, and minimize losses and correct data,
where possible. Independent of any EPA QA activities, Battelle will be responsible for ensuring
that the audits described below are conducted as part of this verification test.
Cl.l Technical Systems Audits
An auditor from the NJDEP OQA will perform a TSA once during this verification test, in both
the laboratory and field testing locations. The laboratory audit will be performed by the NJDEP
according to guidelines provided by the NELAC Institute. The purpose of this audit is to ensure
that the verification test is being performed in accordance with the AMS Center QMP,1 this
test/QA plan, and the published reference method. In the TSA, the NJDEP QA auditor may
review the reference method used, compare actual test procedures to those specified or
referenced in this plan, and review data acquisition and handling procedures. In the laboratory,
the NJDEP QA auditor may inspect the simulated test cells and test procedures, and view data
records. This person also will check calibration certifications for test measurement devices. In
the field the NJDEP QA auditor may inspect USDA site QA records, observe USDA sampling
and analysis procedures, and review data records. The Battelle Quality Assurance Manager will
communicate ETV specific QA requirements to the NJDEP QA auditor prior to the TSA. A
TSA checklist will be prepared by the NJDEP QA auditor which will be reviewed and approved
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by the Battelle and EPA Quality Managers prior to use in the TSA. A TSA report will be
prepared by NJDEP, including a statement of findings and the actions taken to address any
adverse findings. The NJDEP QA auditor will submit the audit report, 10 business days
following the TSA, to the Battelle Verification Test Coordinator and the Battelle Quality
Assurance Manager, who will distribute the report to the EPA. At EPA's discretion, EPA QA
staff may also conduct an independent TSA during the verification test. The TSA findings will
be communicated to technical staff at the time of the audit and documented in a TSA report.
C1.2 Performance Evaluation Audit
A PE audit of the nitrate concentrations will be completed to confirm the accuracy of the
laboratory nitrate analysis reference method (EPA 300.1). The PE audit will be performed by
the Verification Test Coordinator, or designee. Prior to the laboratory and field investigations,
up to five blind nitrate samples will be generated from a stock solution in the laboratory and sent
to the USDA ARS National Laboratory for Agriculture and the Environment. The blind nitrate
sample concentrations will be within the range of anticipated field concentrations. The
associated reported laboratory nitrate concentration values will be verified against the blind
sample concentrations to determine whether the concentration values are within an acceptable
range. Results of the PE audit samples will be compiled by the Verification Test Coordinator
and reviewed by the Battelle Quality Manager who will provide a copy to EPA within 10
business days of receipt of the laboratory report.
C1.3 Audit of Data Quality
The Battelle Quality Manager, or designee, will audit at least 10% of the verification data
acquired in the verification test. The Battelle Quality Manager will trace the data from initial
acquisition, through spreadsheet entry, reduction and statistical comparisons, to final reporting.
All QC data and all calculations performed on the data undergoing the audit will be checked.
Results of the ADQ will be compiled and reviewed by the Battelle Quality Manager who will
discuss findings in a written report distributed to the Verification Test Coordinator and EPA
within 10 business days after completion of the laboratory report review.
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C1.4 QA/QC Reporting
Each assessment and audit will be documented in accordance with Sections 3.3.4 and 3.3.5 of the
AMS Center QMP.1 The results of all audits will be submitted to EPA within 10 business days
as noted above. Assessment reports will include the following:
• Identification of any adverse findings or potential problems
• Response to adverse findings or potential problems
• Recommendations for resolving problems
• Confirmation that solutions have been implemented and are effective
• Citation of any noteworthy practices that may be of use to others.
C2 REPORTS TO MANAGEMENT
During the field and laboratory evaluation, any test/QA plan deviations will be reported
immediately to EPA. The Battelle Quality Manager and/or Verification Test Coordinator, during
the course of any assessment or audit, will identify to the technical staff performing experimental
activities any immediate corrective action that should be taken. A summary of the required
assessments and audits, including a listing of responsibilities and reporting timeframes, is
included in Table 6. If serious quality problems exist, the Battelle Quality Manager will notify
the AMS Center Manager, who is authorized to stop work. Once the assessment reports have
been prepared, the Verification Test Coordinator will ensure that a response is provided for each
adverse finding or potential problem and will implement any necessary follow-up corrective
action. The Battelle Quality Manager will ensure that follow-up corrective action has been
taken. The test/QA plan and final report are reviewed by EPA AMS Center QA staff and EPA
AMS Center program management staff. Upon final review and approval, both documents will
then be posted on the ETV Web site (www.epa.gov/etv).
Table 6. Summary of Reports to Management
Assessment
TSA
PE Audit
ADQ
Responsible
Agency
NJDEP OQA
Battelle
Battelle
Report Submission
Timeframe
10 business days after TSA
is complete
10 business days after
receipt of laboratory report
10 business days after
completion of the laboratory
report review
Receiving Agency
Initially to Battelle VTC and
subsequently to EPA
Initially to Battelle VTC and
subsequently to EPA
Initially to Battelle VTC and
subsequently to EPA
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SECTION D
DATA VALIDATION AND USABILITY
Dl DATA REVIEW, VALIDATION, AND VERIFICATION REQUIREMENTS
The key data review requirements for the verification test are stated in Section BIO of this
test/QA plan. The QA audits described in Section Cl of this document, including the audit of
data quality, are designed to ensure the quality of the data. Data will be verified for
completeness, correctness, and compliance with the procedures as written in this test/QA plan.
D2 VALIDATION AND VERIFICATION METHODS
Section C of this test/QA plan provided a description of the validation safeguards employed for
this verification test. Data validation and verification efforts include the use of a Dionex ICS-
2000, and the performance of TSA and data audits. An audit of data quality will be conducted
by the Battelle Quality Manager to ensure that data review and validation procedures were
completed, and to ensure the overall quality of the data. Any findings will be communicated to
technical staff at the time of the audit and documented in a report.
D3 RECONCILIATION WITH USER REQUIREMENTS
The purpose of this test is to evaluate the performance of nitrate sensors. The data obtained
should include thorough documentation to allow verification of the performance of each nitrate
sensor. The data review and validation procedures described in the previous sections will ensure
that data meet these requirements and are accurately presented in the evaluation reports
generated from this test. Data for which incomplete recording cannot be resolved will be
retained but will be flagged and not used for nitrate sensor verification.
This test/QA plan and the resulting ETV verification report(s) will be subjected to review by the
technology vendors, USDA and EPA, and expert peer reviewers. These reviews will ensure that
this test/QA plan and the resulting report(s) meet the needs of potential users of nitrate sensors.
The final report(s) will be submitted to EPA in Microsoft® Word and Adobe PDF compliant
format and subsequently posted on the ETV Web site.
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SECTION E
REFERENCES
1. Battelle. 2008. Quality Management Plan (QMP)for the ETV Advanced Monitoring
Systems Center, Version 7.0, Environmental Technology Verification Program, November.
2. EPA. 2008. Environmental Technology Verification Program Quality Management Plan.
Version 3.0, EPA/600/R-08/009, January.
3. Vitousek, P.M., J. Aber, R.W. Howarth, G.E. Likens, P. A. Matson, D.W. Schindler, W.H.
Schlesinger, and G.D. Tilman. 1997. "Human Alteration of the Global Nitrogen Cycle:
Causes and Consequences," Issues in Ecology 1: 1-17.
4. Baker, J.L., K.L. Campbell, H.P. Johnson and JJ. Hanway. 1975. "Nitrate, Phosphorus,
and Sulfate in Subsurface Drainage Water," J. Environ. Qual. 4:406-412.
5. Kanwar, R.S., J.L. Baker, and D.G. Baker. 1988. "Tillage and Split N-fertilization Effects
on Subsurface Drainage Water Quality and Crop Yields," Trans. ASAE 31:453-461.
6. Patni, N.K., L. Masse, and P.Y. Jui. 1996. "Tile Effluent Quality and Chemical Losses
under Conventional and No Tillage-Part 1: Flow and Nitrate," Trans. ASAE 39:1665-1672.
7. Jaynes, D.B., J.L. Hatfield, and D.W. Meek. 1999. "Water Quality in Walnut Creek
Watershed: Herbicides and Nitrate in Surface Waters," J. Environ. Qual. 28:45-59.
8. Kladivko, E.J., J.R. Frankenberger, D.B. Jaynes, D.W. Meek, B.J. Jenkinson, and N.R.
Fausey. 2004. "Nitrate Leaching to Subsurface Drains as Affected by Drain Spacing and
Changes in Crop Production System," J. Environ. Qual. 33:1803-1813.
9. Tomer, M.D., T.B. Moorman, and C.G. Rossi. 2008. "Assessment of the Iowa River's
South Fork Watershed: Part 1. Water Quality," Journal of Soil and Water Conservation.
63(6):360-370.
10. Rabalais, N.N., W.J. Wiseman, R.E. Turner, B.K. Sen Gupta, and Q. Dortch, Q. 1996.
"Nutrient Changes in the Mississippi River and System Responses on the Adjacent
Continental Shelf," Estuaries. 19,386-407.
11. Blowes, D.W., W.D. Robertson, C.J. Ptacek, and C. Merkley, C. 1994. "Removal of
Agricultural Nitrate from Tile-drainage Effluent Water using In-line Bioreactors," J.
Contam. Hydro!. 15,207-221.
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12. Schipper, L. and M. Vojvodic-Vukovic. 1998. "Nitrate Removal from Groundwater using
a Denitrification Wall Amended with Sawdust. Field Trial," J. Environ. Qual. 27,664-
668.
13. Schipper, L.A. and M. Vojvodic-Vukovic. 2000. "Nitrate Removal from Groundwater and
Denitrification Rates in a Porous Treatment Wall Amended with Sawdust," Ecol. Eng.
14,269-278.
14. van Driel, P.W., W.D. Robertson, and L.C. Merkley. 2006. "Denitrification of Agricultural
Drainage using Wood-based Reactors," Trans. Am. Soc. Biol. Eng. 49,565-573.
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Appendix A
Conventional Groundwater Sampling Procedures
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Battelle
Environmental Restoration Department
GROUND WATER PURGING AND SAMPLING PROCEDURES USING A
PERISTALTIC PUMP
1.0 PURPOSE AND SCOPE
The purpose of this document is to define the equipment necessary and the standard operating
procedure (SOP) for collecting groundwater samples using a peristaltic pump. This SOP
describes the equipment, field procedures, materials, and documentation procedures necessary to
collect groundwater samples. This SOP also contains information pertaining to the handling of
groundwater samples, decontamination procedures to be completed during groundwater
sampling, and procedures for the management of investigation-derived waste generated during
this activity.
This procedure is to be followed during the ETV nitrate sensor evaluation field investigation, and
any substantive modification to the procedure shall be approved in advance by the Field Team
Leader(s), the Battelle Quality Manager and/or the Verification Test Coordinator, with
subsequent notification of significant deviations to EPA.
2.0 RESPONSIBILITIES AND QUALIFICATIONS
The Verification Test Coordinator is responsible for assigning appropriately-qualified field
personnel for conducting the various activities to be completed at the site. The Verification Test
Coordinator and Field Team Leader(s) is (are) also responsible for assuring that this and any
other appropriate procedures are followed by field personnel. Field personnel assigned to the
various site activities are responsible for completing their tasks according to this and other
appropriate procedures. Field personnel are responsible for documenting and reporting
deviations from the procedure or nonconformance to the Field Team Leader(s). Only qualified
field personnel shall be allowed to perform this procedure. Qualifications will be based on
training, documented previous experience and health and safety training.
3.0 GROUNDWATER SAMPLING PROCEDURES
Groundwater samples will be collected from the bioreactor monitoring wells and from the inlet
pipeline using a peristaltic pump. The following subsections document the procedures
associated with groundwater sample collection using a peristaltic pump.
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3.1 EQUIPMENT LIST
The following equipment list contains materials that may be needed to carry out the procedures
contained in this portion of the SOP. Since multiple discrete activities are described in this SOP,
not all materials on the equipment list may be required for each activity. Equipment used during
groundwater sample collection includes the following:
• Appropriate Level D health and safety equipment (i.e., nitrile gloves and safety
glasses)
• Permanent marker or grease pencil
• 5-gallon buckets
• Field logbook
• Appropriate decontamination equipment (i.e., DI water, Alconox®, and trash bags)
• Electronic water level indicator
• Peristaltic pump(s) (Geotech Series II Geopump variable rate peristaltic pump, or
similar)
• Silicone tubing
• Teflon™-lined polyethylene tubing
• Polypropylene twine
• Laboratory-provided sample plastic ware or certified pre-cleaned plastic ware
• Coolers, ice, ice chests, and/or refrigerated storage unit
3.3 WATER LEVEL MEASUREMENT PROCEDURES
To provide information on groundwater flow and water levels within the bioreactor, depth to
groundwater data will be collected from the monitoring wells and the inlet pipeline. The
following steps will be followed to measure the depth to ground water in a monitoring well:
(1) Remove the flushmount lid or the lid to the stickup well casing.
(2) Remove the compression cap. Listen for signs of vapor lock, which can cause the
groundwater surface to fluctuate until it achieves equilibrium with the atmosphere.
(3) Insert the probe of an electronic water level indicator equipped with a graduated tape.
(4) When the indicator signals contact with groundwater, the depth to groundwater will
be recorded to the nearest 0.01 foot relative to the vertical survey datum assigned to
the well (i.e., the top of casing or ground surface).
(5) If the contact signal fluctuates in a manner indicating that the groundwater surface is
still rising in the well, the reading will not be recorded until the groundwater surface
stabilizes.
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3.4 GROUNDWATER PURGING AND SAMPLE COLLECTION
This section provides the step-by-step procedures for collecting groundwater samples from the
monitoring wells. Observations made during groundwater sample collection should be recorded
in the field logbook.
3.4.1 Purging
Prior to collecting groundwater sample volume from a monitoring well, a minimum volume of
groundwater will be purged to ensure the collection of a representative sample. The following
procedures will be followed to purge a monitoring well:
(1) Fresh silicone tubing will be installed in a peristaltic pump.
(2) The cap will be removed from the dedicated in-well Teflon™-lined polyethylene
tubing.
(3) The dedicated in-well polyethylene tubing will be connected to the inlet end of the
peristaltic pump, and an additional length of polyethylene tubing will be connected to
the outlet end of the pump.
(4) The outlet tubing from the peristaltic pump will be routed to a 5-gallon bucket placed
on a firm and level surface.
(5) The peristaltic pump will be engaged at a minimum sustained operation level and
groundwater will be purged from the well equivalent to one polyethylene tubing
purge volume (based on the depth to groundwater reading)
(6) The purge water will be consolidated as investigation-derived waste and decanted to
ground surface outside of the bioreactor.
3.4.2 Groundwater Sampling
Once purging has been completed, groundwater sampling will be completed as follows:
(1) A "dirty hands"/ "clean hands" approach will be followed during actual sampling as
outlined in U.S. EPA Method 1669 where all operations involving contact with the
sample bottles and transfer of the sample from the sample collection device to the
sample bottle are handled by the individual designated as "clean hands." "Dirty
hands" is responsible for preparation of the sampler (except the sample container
itself) and for all other activities that do not involve direct contact with the sample.
(2) For all analyses the peristaltic pump will remain engaged and laboratory plastic ware
will be filled directly through the pump.
(3) Groundwater retrieved will be slowly added to the appropriate sample plastic ware,
taking care to avoid agitation and air bubbles.
(4) For each analyte, two sample containers will be filled per laboratory requirements and
preserved as/if necessary.
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(5) Samples will be stored on ice in sealed coolers or chests, and/or in a refrigerated
storage container, and checked for preservation temperature of 4°C, pending same-
day delivery to the USDA laboratory.
4.0 SAMPLE HANDLING PROCEDURES
This section defines the procedures for labeling, containerizing, handling and shipping
groundwater samples collected for analysis. These steps are essential, and could affect tracking,
documentation, or integrity of samples. These procedures are intended to provide sufficient
instructions for sampling personnel to follow equally, reliably, and consistently.
4.1 EQUIPMENT LIST
The following equipment list contains materials that may be needed to carry out the procedures
contained in this portion of the SOP:
• Inert packing material
• Sample containers
• Sample labels
• Chain-of-Custody Forms
• Ice chest(s)/coolers
• Marking pens
• Shipping tape
• Sealable plastic bags
• Field logbook
• Ice or similar chilling source
• Paper towels or cloth.
4.2 SAMPLE LABELING
Each bottle used for sampling will have a preprinted label attached that is identical to the
example label shown below. Whenever possible, field personnel will have the project
identification, requested analyses and sample identification typed/printed onto the label before
sampling. The date and time will be added at the time of sample collection. Where necessary,
the label will be protected from damage with clear tape.
Nitrate Sensor ETV Study
Sample ID:
Date: Time:
Analyses:
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Each field-collected sample will be assigned a unique sample ID that is documented on the
sample container label and the field collection log form. This system provides a distinct link
between the sample and the related collection information. Sample identification numbers will
be in the format:
X-DDMM-TTTT
where,
DDMM is the date (day/month)
TTTT is the time (24-hour)
X is the sample location, where:
1 Well 1
2a Well 2 - upper screen
2b Well 2 - lower screen
3 Well 3
IN Test cell inlet
4.3 SAMPLE CONTAINERS AND PRESERVATION
4.3.1 Sample Containers
Certified, pre-cleaned containers will be supplied from commercial suppliers or laboratories for
the collection of all groundwater samples. Sample containers will be cleaned to the quality
control standard defined in OSWER Directive #9240.0-05A. Certification of sample container
quality per the OSWER directive will be kept in the project files. Two 125 mL poly containers
will be filled for each sampling location.
4.3.2 Sample Preservation
No sample preservatives will be added, nor will any sample filtering be required during this
investigation. Samples will be placed on ice after collection, and shipping containers will be
packed with additional ice, if needed, prior to shipment via overnight carrier.
4.4 SAMPLE PACKAGING AND SHIPPING
Sample packaging and shipping will be performed as follows:
(1) After filling, securely seal sample bottle caps and complete the sample labels (if
labels were not preprinted).
(2) Clean the outside of the samples bottles by wiping them off with a cloth or paper
towel.
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(3) Transfer the samples to an ice chest that will be used as a shipping container. For
samples leaving the Site, use inert packaging material to cushion the samples and
minimize the potential for breakage.
(4) If refrigeration is necessary, ice chests or coolers will contain ice or similar chilling
sources sufficient to maintain 4° ± 2°C inside cooler during same-day transport to the
laboratory.
(5) Complete chain-of-custody (COC) documentation, and place appropriate copies of
the documents in a sealable plastic bag inside the ice chest (taped to the inside lid).
Prior to sealing for shipment, the list of samples will be checked against the
cooler/chest contents to verify the presence of each sample listed on the chain-of-
custody.
(6) Transport the shipping container directly to the laboratory. Samples will be shipped
within an appropriate timeframe after collection to ensure meeting all relevant sample
and laboratory holding times.
4.5 SAMPLE TRACKING
All samples collected for analysis will be continuously tracked, in the field and in transit to the
laboratory as follows:
(1) Individual sample bottles will be properly labeled and securely sealed before being
placed in the container for shipment to the laboratory.
(2) All pertinent information will be entered on the COC form in the field (see Appendix
C). COC forms must include the following, as required by guidance in SW-846, Test
Methods for Evaluating Solid Waste (EPA, Third Edition, including Promulgated
Update I, 1993, Chapter One): 1) the project name; 2) signatures of samplers; 3) the
sample number, date and time of collection, preservatives, analyses to be performed,
and grab or composite sample designation; and 4) signatures of individuals involved
in sample transfer.
(3) The completed COC form will be signed, dated, enclosed in a sealable plastic bag and
placed in the container prior to shipment (taped to the inside lid). A copy of the COC
form will be retained by field personnel and an additional copy transmitted to the
Verification Test Coordinator or the Verification Test Coordinator's designee.
(4) Samples will be considered in the sampler's custody while in sight, or locked in a
secure area prior to delivery. If the person packing the container and verifying the
sample list is different than the sampler, both the sampler and the packer will sign the
COC form.
(5) Upon receipt at the laboratory, the designated laboratory sample custodian shall sign
the COC form indicating receipt of the incoming field samples. The samples shall be
checked against the COC form upon arrival at the laboratory. The receiving
personnel will enter all arriving samples into a laboratory logbook and note any
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problems or discrepancies between the samples and COC forms and sample container
and seal conditions and report them immediately to the Verification Test Coordinator.
(6) A copy of the COC form shall be returned from the laboratory to the Verification Test
Coordinator or the Verification Test Coordinator's designee. The original shall be
retained by the laboratory's sample custodian.
5.0 DECONTAMINATION PROCEDURES
This section defines the procedures for cleaning reusable groundwater sampling equipment
sufficiently to ensure that cross-contamination of samples does not occur. These steps are
essential, and could affect the integrity of site sampling data. These procedures are intended to
provide sufficient instructions for sampling personnel to follow equally, reliably, and
consistently.
Throughout sample collection activities, care will be taken to avoid sample contamination. This
will be accomplished through rigorous decontamination procedures and careful sample handling
procedures, as follows:
(1) To the extent possible, non-contaminating materials (e.g., glass, stainless steel or
Teflon™) will be used for groundwater sampling activities.
(2) All potential sources of contamination (e.g., airborne sources, personnel, or unclean
equipment) will be avoided.
(3) To avoid cross-contamination in groundwater samples collected for chemical
analysis, separate, pre-cleaned or new Teflon™-lined polyethylene tubing, silicone
tubing and bailers will be used at each sampling location.
(4) The electronic water level indicator will be decontaminated by spraying the probe
with a solution of water and non-phosphate detergent, followed by spraying with
deionized water.
(5) If possible, gasoline or diesel engine powered equipment will be shut down at least
one minute prior to sampling activities to eliminate the potential for contamination by
exhaust gasses. If this is not possible, samples will be processed up-wind of the
engines and care will be taken to avoid contamination from engine exhaust.
During all groundwater sampling and handling activities, field personnel will don appropriate
personal protection equipment (PPE) (Level D) to avoid contact with potential contamination
and also to avoid cross-contaminating samples. PPE will be changed as necessary to ensure that
cross-contamination potential is minimized.
6.0 INVESTIGATION-DERIVED WASTE PROCEDURES
Implementation of groundwater sampling activities is expected to generate some amount of
investigation-derived waste (IDW). Field sampling and sample preparation activities will be
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conducted such as to minimize generation of waste materials (i.e., residual groundwater). In the
field, trace amounts of residual groundwater from sampling equipment will be temporarily stored
in 5-gallon buckets and decanted to ground outside the bioreactor footprint. All general solid
waste (gloves, paper towels, used tubing, etc...) will be bagged or otherwise contained prior to
disposal in standard refuse containers (dumpsters). Solid waste and wastewater generated during
sample preparation at each laboratory will be managed in compliance with the organization's
requirements.
7.0 FIELD QUALITY CONTROL
During groundwater sampling activities, QC samples will be collected to ensure the reliability of
data.
7.1 FIELD DUPLICATES
Duplicate groundwater samples will be collected at a frequency of one for every 10 samples (i.e.,
10%) for all analytes to evaluate the reproducibility of analytical results. If 10 samples are not
collected during a sampling event, one duplicate sample per sampling event will be collected.
Duplicate samples will be collected simultaneously with the base sample, and will be collected
into identical sample plastic ware. Laboratory plastic ware for a particular analyte will be filled
in alternating sequence between base sample and duplicate. Duplicate samples will be identified
as "DUP" on the sample label.
7.2 MATRIX SPIKE/MATRIX SPIKE DUPLICATES
Matrix Spike/Matrix Spike Duplicate (MS/MSD) samples are used by the laboratory to evaluate
the accuracy of its methods and equipment. MS/MSD samples will be collected at a frequency
of one for every 20 samples (i.e., 5%). If 20 samples are not collected during a sampling event,
one MS/MSD sample per sampling event will be collected. These samples typically require the
collection of triplicate sample volume (i.e., one volume for base sample, one volume for MS and
one volume for MSD), and will be collected into identical sample plastic ware as the base
sample. MS/MSD samples are labeled identically for all volume collected, and will be properly
identified as being a QC sample on the COC. No spiking of the MS/MSD will occur in the field.
7.3 EQUIPMENT BLANKS
Equipment blanks, also referred to as rinsate blanks, are collected to evaluate the potential for
sample cross-contamination from the sampling equipment used. Equipment rinsate blanks will
be collected daily, during sampling, for the groundwater sampling equipment to ensure that
nondedicated sampling devices have been decontaminated effectively. Daily equipment blanks
will be collected after collection of at least one field sample and after the equipment has been
decontaminated. The equipment blank for groundwater sampling equipment will be laboratory-
provided deionized water that is passed through or over the sampling equipment used to collect
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samples (i.e., Teflon™ polyethylene tubing). Each equipment blank will be assigned a unique
field sample identification number, and analyzed for nitrate.
8.0 DOCUMENTATION
8.1 FIELD NOTES
The Field Team Leader(s) or the Field Team Leader(s)' designee(s) is (are) responsible for
documenting groundwater sampling and sample handling activities. Observations and data will
be recorded on the Field Data Sheet (see Appendix C) and stored in the project notebook.
8.2 CHAIN-OF-CUSTODY DOCUMENTATION
All samples will be handled under strict chain-of-custody. COC forms will be provided by the
selected analytical laboratory or will be Battelle's standard COC. Information to be included on
the COC forms, and the procedures for tracking samples through the COC process, are included
in the "Sample Tracking" section above.
Approvals
Author: Date:
Verification Test Coordinator: Date:
Battelle Quality Manager: Date:
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Appendix B
Field Activities Log
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Baneiie
EW NITRATE SENSOR STUDY
FIELD ACTIVITIES LOG
Recorder;
Date:
of
Personnel Present:
Weather:
Time
(00:00)
Activity
FieW learn Leactet Signature
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Appendix C
Field Sampling and Example Chain of Custody Forms
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Batreiie
ETV NITRATE SENSOR STUDY
FIELD SAMPLING FORM
Location.
Date-
Well IO
Start Time End Time
Depth to Water {ft}
Volume PufflccS (ml)
CofWtton of Dedicated Tutjing and Cap
Personnel
Weather
Time Sample Collected
Sample Inlet Depth (ft)
Volume of Sample Cote-etcd (ml)
sigpstiif* of RftcoMsr'
Location1
Dale
Well 10
Start Time End Time
Depth to Water (It).
Volume Purged (ml)'
Personnel
Weather
Tirr» Sample Collected
inlet Depth (ft).
Volume of Sample Collected (ml)-
Cornsiton of Dedicated Tubing and Cap.
N«'es-
S)0i3tufe d Reew-cter,
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EXAMPLE
SAMPLE CUSTODY RECORD
Battellc
Date
of
Project No,:
Prated Name:
Project Manager
Ptione:
Lab No' '
Sample
No,
i
1
|
j
Collection
Date
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Signature Date Tim*
PwttHl tome C^mjanj-
Matrix
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ers
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Prirt^cS IS49r*i6 Co^c*arf>
RceeivMI try
SflMlur* Oil* Tim*
Printed Name Company
« I
J*J
Laboratory:
AtWrew:
Altn:
Observations,
Instftieiions
total io!eiMita»iBS
Slupm^nt Wftfwd
&peci«l RequireiTbei^ts of Oomlitsons:
Otvtrfbutton-
i 2 copse-Si lo Ihe Ul bora toy
3 Return e^rr^i^igd ws^iai to Bane**
Mann® Scserc«s LMKyrator^'
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Appendix D
Nitrate Sensor Implementation Document
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Standard Operating Procedure for the AquiStar® TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
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INTRODUCTION
What is the TempHion™ Smart Sensor?
The AquiStar® TempHion™ Smart Sensor is a
submersible water quality sensor and datalogger capable
of measuring pH, specific ions, redox, and temperature.
Each unit comes with a thermistor based temperature
element plus a combination of pH, ISE, or redox
elements. (Contact INWfor available combinations.)
The TempHion™ Smart Sensor is powered internally
with two AA alkaline batteries or with an auxiliary power
supply for data intensive applications. The unit is
programmed using a laptop or desktop Windows® based
computer via its RS485/RS232 adaptor and TNW's easy-
to-use Aqua4Plus software. Once programmed, the unit
will measure and collect data on a variety of time
intervals.
Several TempHions, or a combination of TempHions and
other INW Smart Sensors, can be networked together and
controlled from one location, either directly from a single
computer or via a WaveData® Wireless Data Collection
System.
The internal processor in the TempHion™ Smart Sensor
allows for easy calibration, using the calibration utilities
in Aqua4Plus. Once calibrated, this calibration data is
stored in non-volatile memory within the Smart Sensor.
When data is collected, this calibration information is
applied to the data, resulting in highly accurate readings at
a wide range of temperatures.
Initial Inspection and Handling
Upon receipt of your smart sensor, inspect the shipping
package for damage. After opening the carton, look for
concealed damage, such as a cut cable. If damage is
found, immediately file a claim with the carrier. Check
the label attached to the cable at the connector end for the
proper cable length.
Do's and Don'ts
Do handle the device with care.
Do store in water or calibration solution and keep vertical
once filled with reference solution.
Don I install the device so that the connector end is
submerged.
Don I support the device with the connector or with the
connectors of an extension cable. Use a strain relief
device to take the tension off the connectors.
Don t allow the device to free-fall down a well as impact
damage can occur.
Don "t bang or drop the device on hard objects.
Theory-in-Brief
TempHion works on the principal of direct potentiometry,
i.e., the same principal that governs airy other pH or ISE
electrode. In direct potentiometry, two electrodes - a
sensing electrode and a reference electrode - are
immersed in the solution that is being analyzed.
TempHion is a "combination" electrode, which means
that both the reference electrode and the sensing electrode
are contained in one instrument body. (The majority of
modern pH and ISE electrodes, particularly those
intended for portable field use, are combination
electrodes.) Together, the two immersed electrodes are
analogous to a dry cell used to power a flashlight. To use
or to measure the potential (voltage) of a dry cell,
electrical connections must be made to both the positive
and negative poles. The voltage measured is the "cell
potential" and represents the difference between the
electrochemical half-cell potentials of the two poles. lii
direct potentiometry, the two poles of the cell are
represented by the sensing and reference half-cell
electrodes.
The half-cell potential of a sensing electrode varies
logarithmically with the concentration of the ion it is
designed to sense. The reference electrode is designed to
maintain a constant half-cell potential, against which the
half-cell potential of the sensing electrode is measured.
The most common type of reference electrode used for
pH/ISE measurements consists of pure silver metal coated
with a layer of silver chloride (usually identified as a
Ag/AgCl reference electrode). This is identical in
concept (but not in construction) to the chloride sensing
electrode used with TempHion. The constant half-cell
potential of the reference electrode is established by
immersing the solid state Ag/AgCl reference element in a
solution of known and constant chloride content, known
as the reference electrode filling solution. The reference
half-cell potential will remain stable if the filling solution
is in no way altered by contamination or dilution, which
means that the capillary thread must maintain its integrity.
The filling solution must be in direct contact with the
solution being tested to allow ionic charge transfer.
Conventional reference electrodes designed to be
submerged or under pressure typically use a ceramic or
semi-permeable membrane to allow ionic charge transfer
while at the same time acting as a physical barrier keeping
the test solution and the filling solution from
Instrumentation Northwest, Inc. www.invvusa.com infojojinwusa.com
8902 122nd Avenue NE, Kirkland WA 98033 (425)822-4434 Fax (425) 822-8384
4620 Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997 - 2009 by Instrumentation Northwest, Inc. Doc#9B0812r2 04/10 Page1of15
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intermingling. These electrodes are electrically resistive
and prone to fouling. While they are usually initially
stable and accurate, fouling quickly leads to a noisy and
unstable signal.
TempHion uses a long capillary pathway, initially filled
with reference electrode filling solution, to separate the
reference electrode chamber from the solution being
analyzed. In addition, TempHion's reference electrode is
filled without any air (which is compressible). With this
construction, the principle mechanism that will eventually
allow test solution to enter the reference chamber and
contaminate the reference electrode filling solution is
diffusion - an exceedingly slow mechanism. Further,
while the capillary pathway is narrow by garden hose
standards, its open cross-section is huge compared to the
microscopic openings in a conventional porous ceramic
fluid/fluid junction. It is therefore much less susceptible
to fouling. Fluid expansion and contraction caused by
temperature variations can augment the effects of
diffusion. Nevertheless, TempHion's proven stability
under actual field conditions is measured in weeks or
months, rather than hours or days!
Figure 1 illustrates the construction of the TempHion™
reference electrode. Please note that the capillary
pathway between the reference and test solutions is
established using a modified screw thread. This means
that the capillary can be easily opened up for cleaning,
refilling, or other maintenance.
Liquid Junction Port
Outer Reference
Housing
Reference
Electrode
Assembly
Capillary Flowpath
(Modified Thread)
Reference Electrode
Filling Solution
Reservoir
Reference Element
Figure 1: Reference Electrode Assembly: The modified
thread provides a continuous liquid path between the
solution in which the instrument is immersed and the
reference element.
General Precautions
The rest of this document includes step-by-step
instructions for setting up the TempHion™, calibrating it,
and using it in the field. When reading and following the
instructions in these sections, keep these very important
considerations in mind:
• Do not handle the surfaces of the sensing electrodes.
Oils from fingers can "blind" the reactive surface.
Rough handling can scratch the reactive surface.
• Avoid long-term exposure of silver-based sensing
electrodes to bright sunlight.
• Use calibration standards that are accurately
prepared. Discard standards after use. Do not
return the used standards to the bottles of "fresh"
solution.
• When TempHion's reference electrode contains
filling solution, TempHion must be stored in water to
prevent evaporation of the filling solution.
• For any step-change in temperature (e.g., where
calibration standards are at a different temperature
than water to be tested) allow the instrument to come
to complete thermal equilibrium before making
measurements. Up to 30 minutes may be required.
SETUP AND INSTALLATION
Care and Filling of Reference Solution
Reservoir
The TempHion's patented reference electrode is key to
the TempHion's superior performance. The TempHion
uses a long capillary pathway, filled with reference
solution, to separate the reference electrode from the
solution being analyzed. Proper care and filling of this
reference solution reservoir is essential to accurate
functioning of the sensor.
The TempHion is normally shipped with a bottle of INW
Reference Solution. If you will be using a different
solution, contact INW for any adjustments that may be
needed.
Emptying and Cleaning the Reservoir
The TempHion is shipped fully assembled with the
reservoir empty and the reference electrode chemically
clean and dry. If you have just received your sensor from
INW, you will not need to empty the reservoir. You
should still, however, follow the instructions below for
cleaning the electrode and reservoir cap.
Instrumentation Northwest, Inc. www.inwusa.com info@inwusa.com
8902 122nd Avenue NE, Kirkland WA 98033 (425) 822-4434 Fax (425) 822-8384
4620 Northgate Blvd.» 170, Sacramento CA 95834 (916) 922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc#9B0812r2 04/10 Page 2 of 15
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Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor - pH, ISE, Redox (April 2010)
• Unscrew Iht reservoir cup. Do oof touch or uniith
UK viimi*: hnitimi or Hie rclrrenrr electrode!
* I1 mii'y iiii) [fMiiiitiiiii; filling ^wUilkm front UK- cap.
* Tticrauj^hly rinxe HIE reference etectrtxle aid the
inside of Iht cap with distilled or de-ionized water.
• There may be some crystallized residue inade the
cap. on the electrode screw palti. a on the electrode
ilHe[C I] liuttuu dots not clear I hi;- aw ay. 111 MI veuUy
ast a cotton swab or a soft toothbrush to remove tbe
residue.
• Rinse Iht electrode assembly and cap thoroughly
njcaiii Bller tlt-aiiinu. with Uie swab or Iwnsti
• Citntly, pal dry1 with a titan paper lowtl.
,
A
CAUTION Fling saluKsns «e i»i
;•: r.;id4r«l ftazarOiuS , but th*y can b*
irntaJing lo Ih* * kin Prol«d«* glov«
are advised Rtnaa hands or gloves
wiin lr«sh water
2: Canjul nrwagofthe tlKtrode and rfjfrr&r
cap ts) remove any cowTamrnadon is txsiMtaljbr proper
Filling the Reservoir
Once [ht- reservoir hfts becfi enipEted aricL deaitnE, you arc
rtttfy to fill Hit reservoir with reference solution.
• Rinse the reference d ectiodt *sseinUy and Hit iaade
ol Iht nip with a small ainuuul of Hi* reference
solution.
« Miifiiy any U'inainin;n solutioa riom Hie cap.
• Fill cap about half full with reference solution.
• Htilibni! SMISIW vrrlically. rqilace reswvalr c*p.
Some NaltitLDn shixjlcl mrt Im]>|ir4l. u proper Hertrlrol
(ixiiiefiKni c«nn«l tie made and the tensor »m>
I f. r-l 1 1 i ,ir N • ill •. :
• Once filled, keep the sensor upright in liquid 1o
prevent the soliittori from drying out. A I to 10 ppm
dilute chlonde »olntLon is recommoultd, but top
water will do. If you cannot keep seneor in liquid.
tff in slnirtians below for slori nn di}'.
i- &xctss filling wJufjpfl spills cvtr « jft» cap a
tigbteneit.farcing out aty air tubbtet.
Storing Sensor
belefl
FCH tnriB.-1trTii ^tcTBUje, or when Ilic
in liqiBd. the Ktisot should hi- .-lweral monllif lo o year whtn lakinv sxnplef tvejy 15
minutes. Actual battery lift may depend on battery brand,
battery ayu. ltin]*Mlijif of the environment,
c. and oilier lac-lurs.
S|K'. even If the ItrnpHlrin U not ytt
deployed. Heavy recording scbedul ct> cm decrease that
lile. Ihouah you should be able to get al least 20 days of
lifejn rikci>1 drcunuHance^.
Cttattging Batteries
Because dianpinp the balterics involves opening the
v\ a'-. I-IIL-II: --'.ill ll»iv niHSI be done in H deuci, drv
entdrvnmenl lo avoid coaliBilnullon or niolMnrr
I|:.IHI:I:J- to the ui i Mid >.
lnitnjm»ntatl«n Morthw«tt, Int. mm* imusa
8902 123nd Av*nu# WE. KiiKlattJ WA.980J3 (425 ) S22-4434 F«» (425) 623-
4620 Noith^ate Blvd • 170, Saoramerto CA 9S844 (916) 92J-MOO Fa. [916)6
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Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
H-.iirn v
: Two standard AA Alkaline batteries.
ihr l>»l(fritt: Opm the housing by reinovin $
Hie t«^>-ca[3, ii.-; oidlinett t>dow. The top-cap is the
conntctot htrwetn Iht hjht hwhinft, tht sensor and 111*
cable.
1. Twiding genily. unstfew lhdop-c»p.
i. GcnClv separate lilt lop-cap from the bodv of QIC
yenKcr. Tap- cap iMtiuius attached to hotty via
several colored wi res.
Cjuri on ! Ptilli us lor ct-ftilly on the lop-cap can pul I
the inades out ol Ihc sensor or map Hit
cdintcliems iiusiclt. Reciifyi'in^ Iht ciraiil bcKircl ar
pu^iiinit an Hit surfnf* of the nrt^aift tltnieiil may
V trill ;. I'm v, :;i i JMI ••
Note O-ringi provide a WBter-lijtht sell for Ihe
sensor bousing. Take rare no4 to rikk cr Dtlierwbe
ctainuxe ihtse O-TKIS?.^
3. 'Up liauii us over ami gently Jidc bHlttilt » CHJl.
4. liiseri iit-w latll'Hes - podtH'F iFfiuiiLiilv
Ihclop c>p-
_'. Replace and rc4igbtcn top-cap.
.• Oftsly »pam« eA* to
tfif JIT nror. Top-cap remains atta
colored wins.
dy via stvfral
figure 4b: Stide tmaentsoui,
Extamal Power
The Tcnipiiioii can be powered ban in external power
JUIiftly, if deartd 'I'wtlvt vdl power siniplita are
available linn FNW. Alttnuldy, you can connect any
6-13 VIM' aippfy Ihal tan (»nvidc 15 mA. (.'OIBIW:! to
Vniix-^' {while) and (.iround (hliiei or contact INW for
ausaliaiy power connctlorsL
Computer Cottnectian
llie TtnipKion conuecti lo •» IV tilhtr via 3 serial poit or
via a USB perl. The Smirt Seii-ra table i» trnninskd
with a weatherproof connector. For a serial port
LHriMtLlMiri. cmnect Ihe wentlu-rjHaoJ c4xiii«da to ymr
PC oi laplop serial port via the interface cable and an
.'*.si3J adapter, a? *own bdow.
: Connect the
-.:. .: •:,-rproefcott>KCt$rtei few PC0r laptop serial port
vta the tntfrfset coble and an 8S4$3fRS232 oiapttr,
For a USB connection, connect the weslherprool'
coruicclor to your PC or laptop USB port via trie interface
Instrumentation WorthwesMnc
s-M: !?3nd Av»nu»N£. KfMand WA98033 («25)822-«34 F«
4E20 N«thgate B)vd * 170, Sacramento CA 953M <9tS) 922-2800 Fax (916) MS-77S6
. me Doc#9BQ8t2r2 cwno
-------
Standard Operating Procedure for the AquiStar Tempi-lion™
Smart Sensor- pH, ISE, Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 69 of 84
Version 1.0
April 23, 2010
cable, an RS485/RS232 adapter, and an USB to Serial
Cable, as shown below.
Weather-
resistant Interface
Connectors Cable
> — n ra-' HI — ' — 1 1 1
USB port
Sensor
Cable --
PC or Laptop
Comp uter
^ Sensor
Figure 6: USB fort Connection: Connect the
weatherproof connector to your PC or laptop serial port
via the interface cable, an RS485/RS232 adapter, and an
USB to Serial Cable
USB-to-Serial cables are readily available from many
electronics and computer stores, as well as numerous sites
on the Internet. INW has tested and recommends the
Keyspan USA-19HS. It is available from INW or on the
Internet. Install as follows:
• Plug into USB port
• Install the drivers provided with the particular unit
• Note new COM port number. (Right click on My
computer. Select Manage. On left panel click on
Device Manager. On right panel double-click on
Ports. The new COM port should be listed.)
• Connect to the smart sensor (See Figure 6 above.)
• On the Aqua4Plus software, select the COM port
noted above.
Aqua4Plus Software Installation
The TempHion™ comes with the Aqua4Plus host
software to be installed on your PC or laptop. Use this
software to calibrate the sensor, to program the
datalogger, to retrieve data from the logger, to view
collected data, and to export data to external files for use
with spreadsheets or databases. Refer to the Aqua4Plus
software manual for details on installing and using
Aqua4Plus.
Calibration
Overview
The TempHion has two temperature channels and four
millivolt channels. The millivolt channels can be
configured to measure pH, redox, or various selected ions.
Before leaving the factory, your sensor has been
configured specifically for you. All unneeded channels
have been disabled, and the active channels have been
pre-configured. Disabled channels will not display in
Aqua4Plus.
All active channels can be calibrated in the field
Temperature channels rarely need calibrating, however
the millivolt channels should be calibrated before first use
and every one to six months thereafter. It should also be
calibrated if moving to a different sampling environment
where readings will be significantly different than the
current environment.
Environmental conditions of turbulence and temperature
swings, as well as local likelihood for bio-fouling or
mineral deposition, can vary considerably from site to
site. Therefore, where the sensor is to be used for long-
term monitoring, it is recommended that the calibration be
initially checked frequently until a performance history is
established
Aqua4Plus provides an easy-to-use calibration calculator
for performing one- or two-point in-field calibrations.
Two-point calibrations are more accurate and should be
used whenever possible. A Calibration Kit is available
from INW, which includes a beaker, pipette, measuring
beaker, and stand.
In order forthe TempHion Smart Sensorto
calibrate and function correctly, the filling
solution reservoir must be properly filled with
reference solution. See previous section on
filling reservoir.
For best results, the filling solution reservoir
should be filled at least 16 hours before
calibrating.
The sensor and all calibration buffers and
solutions should be at the same temperature
before and during calibration
Calibration can only be done when there are no
sessions stored on the sensor. Ifthere are any
sessions stored on the sensor, upload any data
you want and then erase the sessions before
continuing. (Sessions Menu | Erase All
Sessions)
Instrumentation Northwest, Inc. www inwusa.com infoiSjinwusa.com
8902 122nd Avenue NE, Kirkland WA 98033 (425) 822-4434 Fax (425) 822-8384
4620 Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc#9B0812r2 04/10 Page5of15
-------
Standard Operating Procedure for the AqutStar TempHion™
Smart Sensor - pH, ISE. Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 70 of 84
Version 1.0
April 23, 2010
ReM Calftxvtion Window snd Cafcw (afar
Reid ealihukin ispefftmaienlOT each channel separate!}'.
To calitiraBe a specific chaainel* s«Ie«5 Field Catitsratirai
from the Conll^ire Menu, and ih*n diet on 1ti* dunntl
to be cmlilwatot. Follow directions bdow few i-;icli specifis;
channel type.
Temperature Channel Calibration
The taiipenhire tfcmurf tatty needs falitjeatioo. If
needed. select Fids! Calibration from Ihe Configure
Menu. Click on Temperature. wd Ilini follow Die
iiis^rueliai is on llie screen.
pH Channel Calitxatton
Preparing
* INW recommends pH buffers of -I, "! . and 10 fot
calibration. Fa a cite-point caiibnitjon. srlctt flit
ijiiffer clewed to Ilie «xpetied vaiuesiin yoiir ssiiiples.
Far a Iwo-poinl cajibrattm, select ttw two buffers
ttnl tno:-t cl(X-d> In ackct the expected values in yarn
satiaple^.
* For beS rtadls, took up the buffer's actual pH for the
clc^swl to Iht buffer }en^>CTafurt Ajfiri^
TMs infontialiwi is aviilabJe frrtii Bis
One-Point Calltafatlon
lirM ( »liliralii>n Pninl
Kinst sw.wr Orst with i:i ul , enter Uic
rrf«w»ct pH as noted in the prepaialiai section
above.
did: fits! WftiHtrt button.
• %Vh«ti readings bivt slibilizcd to ymu
click tilt OK btilton in Ihr pop-up box.
Applvlaiu CiiUhruliiin \ ulun
I valut in slit- ncht hna hufftr
* i':ui.-,i- :-tii-«i first with dffilltd water and Utcn with
small amounl of first buffer.
• Plat* comer in bUtTo. (TJuflrr muM be dwp enough
to cover tht sensing bulb in the do4 in Iht M«fc
module CTI Ihe scnidr.)
« AHlowliinefor «nscir to stabilize.
- In the K^f j>fi b«K far th In the KffpH b(K for !h« leoofltd poim, enter ft*
reference |il! m noted in the preparation section
abovt.
» Click iw«id JHfOturr button. (Note: niaairtd
tempt-rilwe must be +/- 1 degree of first measured
tempenfire or caljtmtion will not be accurate!)
• \\lim readinp have Saliliicd ID your satisfartioa
dick ehe OK bwctan in the po|>-i^p box.
« obs«rve the M and / value* in the righl hand §«tion
ol Ihe caloMntor. M diould be brrween -50 and *60.
and I should be between 1 Wind 380.
Instrumentation Morthwest, Inc ^_
~
-------
Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 71 of 84
Version 1.0
April 23, 2010
• Click the Apply button to apply calibration values.
• The reference values, the computed M and I, and the
sample temperature will be transferred to the
calibration fields.
• Click OKto save the values to the sensor.
-Verifying Calibration Values--
• Using the Real Time Monitor, take a few readings
while the sensor is still in the buffer. Be sure units
are set to pH. Readings should be very close to your
selected buffer.
ISE Channel Calibration
(For Nitrate calibration see Nitrate Addendum at end)
Introduction to ISE Calibration
INW recommends using the "known addition method"
for preparing calibration solutions. Using this method,
the sensor is placed in 100 mL of distilled or de-ionized
water. A small amount of standard is added to create a
known concentration. The first point is measured. An
additional amount of the same standard is added to
create a second known concentration. The second point
is measured
INW recommends the calibration standards listed
below. The following instructions are based on using
one of these standards. If you use different standards or
prefer not to use the known addition method, you must
use some other method to determine the concentration
used for the first and second point when calibrating.
Recommended Standards
Bromide
• Molar NaBr (equates to 7990 ppm)
Chloride
• Molar NaCl (equates to 3.550 ppm)
• 100 ppm
• 1000ppm
Preparing
• Select a standard that you will be using for
calibration.
• Place 100 mL of distilled water in a beaker.
Note: Temperature of the water must remain lite
same throughout the calibration. Temperature of the
sensor must also be this temperature prior to
calibration.
One-Point Calibration
—Computing Calibration Value
• Rinse sensor with distilled water and pat dry.
• Place sensor in beaker of distilled water, as
prepared above. (Solution must be deep enough to
cover the sensing buttons.)
• Add 1 cc of selected standard to the water.
Depending on which solution you are using, this
will result in a concentration as shown below:
. 0.1 Molar NaBr (Bromide) = 79.10 ppm
• 0.1 Molar NaCl (Chloride) = 35.15 ppm
« 100 ppm (Chloride) = 0.99 ppm
. 1000 ppm (Chloride) = 9.90 ppm
• Stir to distribute standard evenly.
• Allow time for sensor to stabilize (15 - 20
minutes).
• In the Ref ppm box for the first point, enter the
concentration you have chosen.
• Click the first Measure button. (Readings will be
in mV).
• When readings have stabilized to your satisfaction,
click the OK button on the pop-up box.
Applying Calibration Values
• Observe the/value in the right hand section of the
calculator. For Bromide, I should be between 0
and40. For Chloride,/shouldbebetween 120 and
160.
• Click the Apply button to apply calibration values.
• The reference value, the computed I, and the
sample temperature will be transferred to the
calibration fields.
• Click OKto save the values to the sensor.
-Verifying Calibration Values-
• Using the Real Time Monitor, take a few readings
while the sensor is still in the standard. Be sure
units are set to ppm. Readings should be very
close to your selected concentration.
Two-Point Calibration
—First Calibration Point—
• Rinse sensor with distilled water and pat dry.
• Place sensor in beaker of distilled water, as
prepared above. (Solution must be deep enough to
cover the sensing buttons.)
Instrumentation Northwest, Inc. www.invvusa.com infojojinwusa.com
8902 122nd Avenue NE, Kirkland WA 98033 (425)822-4434 Fax (425) 822-8384
4620 Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc#9B0812r2 04/10 Page7of15
-------
Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 72 of 84
Version 1.0
April 23, 2010
• Add 1 cc of selected standard to the water.
Depending on which solution you are using, this will
result in a concentration as shown below:
. 0.1 Molar NaBr (Bromide) = 79.10 ppm
. 0.1 Molar NaCl (Chloride) = 35.15 ppm
• 100 ppm (Chloride) = 0.99 ppm
• 1000 ppm (Chloride) = 9.90 ppm
• Stir to distribute standard evenly.
• Allow time for sensor to stabilize (15 - 20 minutes).
• In the Ref i>f>iii box for the first point, enter the
concentration you have chosen.
• Cli ck the first Measure button.
• When readings have stabilized to your satisfaction,
click the O/fbutton on the pop-up box.
-Second Calibration Point-
• Add 10 cc of me name standard to the water.
Depending on which solution you are using, this will
result in a concentration as shown below:
• 0.1 Molar NaBr (Bromide) =791.8 ppm
• 0.1 Molar NaCl (Chloride) =351.8 ppm
• 100 ppm (Chloride) = 9.9 ppm
• 1000 pprn (Chloride) = 99.0 ppm
• Stir to distribute standard evenly.
• Allow time for sensor to stabilize (15 - 20 minutes).
• In the Refppm box for the second point, enter the
concentration you have chosen.
• Click the second Measure button.
• When readings have stabilized to your satisfaction,
click the Olfbutton on the pop-up box.
-Applying Calibration Values—
i Observe the M and/values in the right hand section of
the calculator. M should be between -50 and -60. For
Bromide, / should be between 0 and 40. For Chloride,
/should be between 120 andlSO.
< Click the Apply button to apply calibration values.
' The reference values, the computed M and /, and the
sample temperature will be transferred to the calibration
fields.
> Click OK to save the values to the sensor.
-Verifying Calibration Values-
• Using the Real lime Monitor, take a few readings
while the sensor is still in the standard. Be sure units
are set to ppm. Readings should be very close to your
selected concentration.
Redox Channels
Call INW for instructions the first
time you calibrate a TempHion
redox channel.
Note on units: The unit "Eh" refers to readings in
millivolts referenced to a hydrogen
electrode. In other words, Eh represents
millivolt readings that would have been
obtained if using a hydrogen electrode.
The units "mV" are direct millivolt
readings from the sensor.
-For Calibration You Will Need-
• A beaker or bucket of a sample that is representative of
what will be measured with the sensor.
• An alternate redox meter - such as an Orion or YSI
meter.
• Distilled or deionized water.
• Paper towels.
—Computing Calibration Value—
Note: When calibrating a redox channel, do not use the
built-in calculator in the Field Calibration Window.
Instead, follow the instructions below.
1. Rinse sensor with distilled or deionized water,
and then pat dry with clean paper towels.
2. Place the sensor in sample. (Solution must be
deep enough to cover the sensing bulb.)
3. Using the alternate meter, take a redox
measurement of that sample. Use either plain
mV or Eh, whichever you normally use.
4. In Aqua4Plus - set display units to either mV or
Eh, which ever you used for the above step.
5. Scan for and click on the sensor.
6. Open the field calibration window (Configure \
FKblCal&ralmn).
7. Click on the redox channel, and then enter a zero
in the offset box.
Instrumentation Northwest, Inc. www.invvusa.com infojojinwusa.com
8902 122nd Avenue NE, Kirkland WA 98033 (425) 822-4434 Fax (425)822-8384
4620 Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc# 9B0812r2 04/10 Page8of15
-------
Standard Operating Procedure for the AquiStar® TempHion™
Smart Sensor-pH, ISE, Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 73 of 84
Version 1.0
April 23, 2010
8. Click OK
9. Take two or three single readings using the Real
Time monitor and note the reclox value.
10. Subtract this value from the value read in the
step 3.
Applying Calibration Value
11. Open the field calibration window.
12. Click on the redox channel, and then enter this
value in the offset box.
13. Click Off.
-Verifying Calibration Values-
14. Take another couple single Real Time readings.
These should be close to the reading taken with
the other meter.
Field Deployment
Once the TempHion™ Smart Sensor as been calibrated, it
should be stored vertically in water or a calibration
solution until it is placed in service at the field site.
1. Lower the sensor to the desired depth.
2. Fasten the cable to the wellhead using tie wraps
or a weatherproof strain-relief system.
3. Secure the supplied cap on the weatherproof
connector at the top of the cable.
Note that for shallow installations the liquid in which the
sensor is submerged must, at all times, reach high enough
to touch the metal tubing on the sensor.
Do not install such that the connector might become
submerged with changing weather conditions. The
connector can withstand incidental splashing but is not
designed to be submerged.
"\Comniuftiestion
port
Sensor
: 7>ptf of ltulatlatk»i
OPERATION
Data Collection
Following is a brief overview on using Aqua4Plus to
collect data. Please refer to the Aqua4Plus Instruction
Manual for further details on configuring and using
Aqua4Plus.
Real Time Monitor
• Click Single to get a single reading.
• Click Start to get a reading once a second.
• Click Stop to stop the reading.
Note: These are snapshot readings and are not
recorded on the sensor.
Additional Details
Status:
Seuion;
Date I Time | Tempera! Lire[degC) | pH(pH]
15-Feb-05 9:
15-Feb-D5 9:
15-Feb-Q5 9:
15-Feb-D5 9:
^15-Feb-05 9:
3:51
152
3:53
3:54
3:55
20.0
20.0
20.0
2G.O
200
9.300
9.801
9.801
9.000
9.300
Figure 9: Real Time Monitor: Use the Reed Time Monitor
to view live readings from the sensor.
Setting up a Oate Recording Session
Click Ihc 'pfl Uiul buuun. A Session Profile Wintkw will
open. Reftf to Uic Aifaa^Plu.t Instruriiuii Mmiuii} for
details in describing yo*ir session profile. Old; UK Slart
button lo save die session In the sensor and begin
recording.
Instrumenlanon Northwest, Inc. www inwu*a com mtaBmwu^a com
flllll, 8902 122nd AVMU* WE. Kjtkland W S9033 (425) 822-4434 Fta (425) 822- 8384
JOWj 4620 Northgate Blvd. * 170, Sacramento CA 96834 1916} 922-2900 Fax (916) 648-7766
•it697 - 2009 by lnslrum»nt«ha«i NarltiwMt. Inc. Dot* B&08l2r2 (M/10 Pag* ti of 15
-------
Standard Operating Procedure for the AquiStar*TempHion™
Smart Sensor - pH, ISE, Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 74 of 84
Version 1.0
April 23, 2010
/''rgiwY /£?, .VfvjTon f'rttfifo ll'mdow ,-f .uujian p-o/r/tf if a
Jvscrifftftm trftfw tvst steps nteiasary fttr a ptirticitittr
MBC
Retrieving Data from tt>t Sensor/Datalogger
' CLiii, I'll UK lesiviL'n yvu vnuil
• riicfcr1»H|3 irwlbutmn
* Sdcci a nie l
• Click Save.
• Click Sian.
I/.' Click on rht union yov worn u> upload
Viewing Omtt
• rlick I)K Fj iiwl bunon lift vi *w ttir.i ,xi .1 t
• Click UK IE! (wl buttoii 10 view data IB a jiiaph,
lo itic desired t"il«. ihen dick ihc Opot
button (If llw File Open bwc do<* not jpp«r, did:
the I;]J« Mv-nu. (Iwn «k-et Open )
j-igaret?# Tftr /•>/* Htspfay (Cinrfmr tiupftn* ttaln thaf
has hfari uptaadvti hi a afa&jile
I'igurit i3, li;t apfoadtd data eon olio bt dljplafvd in a
graph windmv
Exporting Data to .csv or .xis Files
• lisinp rhc File nis|da>' windi>w,. ffen Ihc file
wait us «jxvn
- Click i>n tlit fl k-rfbulltm
- Sdcet a Ilk W-i4iiii mil] cntn » IKIIIIC (n HIT file
- SdcvtH
(rwlrumerrtatlon Northwest, Inc. www inwjia ram
6902 1
4620 Northgate B)vd * 170, SaeramertO CA 96SM (916) 922-2900 Fax (918)648-7786
, inc Doe* 980Si2r2 CWfl 0
-------
Nitrate Sensors
Test/QA Plan
Page 75 of 84
Version 1.0
April 23, 2010
Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
A Word About Units
Readings from the TempHiotr'^ Smart Sensor can be
displayed in various units. Select the units you want from
the Options | Units menu.
pH: pH or mV
ISE: ppm or mV
Redox: mVH or mV
Temperature: Degrees Celsius, Fahrenheit, or Kelvin
When using pH, ppm, or mVH units, all readings are
automatically compensated for temperature and all field
calibration factors are applied. When using millivolts or
ohms, only the actual millivolt or resistance values are
displayed - no adjustments are made.
lnstrum*ntalsan ttorthwest Inc
-------
Standard Operating Procedure for the AquiStar Tempi-lion1
Smart Sensor- pH, ISE, Redox (April 2010)
Nitrate Sensors
Test/QA Plan
Page 76 of 84
Version 1.0
April 23, 2010
APPENDIX
Wiring Information
Cable Type: 9-conductor, shielded
Shield
White
Brown
Orange
Blue
Yellow
Purple
Ground
Vaux (6 to 13 VDC)
Digital out
Vbat+(1.8 to 3.3 VDC)
Ground
CommD+
Comm D-
Operating Specifications
Accuracy (typical) ± 0.2 pH units
Resolution 0.001 pH units
ISE
Accuracy (typical) ± 5% of reading
Resolution 0.1 ppm
Redox
Accuracy (typical) ± 5% of reading
Resolution
Temperature
Accuracy
Resolution
Time
Accuracy
0.1 mVH
±0.5°C
0.1° C
± 6 sec/day ±2 sec/day (typical)
Recommended Operating
Temperature Range 0°Cto40°C
Contact factory for extended
temperature ranges.
Mechanical Specifications
Sensor
Length:
O.D.
Body Material
Seal Materials
Reference Electrode
Reference Electrolytes
Thermistor
pH Electrode
Chloride Electrode
Bromide Electrode
Nitrate Electrode
Redox
Cable
OD
Break Strength
Weight
Power Supply
Internal
Auxiliary
13.25" to 17.25" depending on
configuration
0.75"
Delrin® and316 stainless steel
Viton® and Teflon®
Patented capillary liquid
junction with Ag/AgCl
electrode
TempHion - no heavy metals
and non-contaminating
SOKOhm
General purpose glass
Solid state
Solid state
Membrane
Platinum Ring
0.28" maximum
13S Ibs.
4 Ibs. per 100 feet
2 AA Alkaline Batteries
6 -13 VDC, 15 Ma
Instrumentation Northwest, Inc. wwvv inwusa com infujojinwusa com
8902 122nd Avenue ME, KirklandWA 98033 (425) 822-4434 Fax (425)822-8384
462° Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc#9B0812r2 04/10
-------
Nitrate Sensors
Test/QA Plan
Page 77 of 84
Version 1.0
April 23, 2010
Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
NITRATE CALIBRATION ADDENDUM
(Letters in parentheses refer to screen shots on last page.)
1. Lab Computation of Slope and Offset (M & I)
a. You will need DI water, 2 molar ammonium sulfate as ionic strength adjuster (ISA), 100 pprn N-NO3
standard NOTE: all liquids must be at the same temperature, as must the sensor, during calibration.
b. Preparation
i. Set Aqua4Plus to display ISE results in ppm.
ii. Prepare a beaker with 100 ml of DI water
iii. Add 1 ml of ISA (Ammonium Sulfate)
iv. Add 1 ml of 100 ppm N-NO3 standard to make a 0.98 ppm solution.
c. Slope and Offset for 1-10 ppm
i. Place sensor in prepared solution and allow to stabilize.
ii. From the Configure Menu, select Field Calibration
iii. In Field Cal window, enter 0.98 in 1st reference box(A).
iv. Click 1st measurement button(B). Click OK on popup when stable(C).
v. AddlO ml of 100 ppmN-NO3 standard to increase solution to 9.82 ppm.
vi. Enter 9.82 in 2"1 reference box(D).
vii. Click 2™* measurement button(E). Click OK on popup when stable(C).
viii. Note the new slope-M to the right(F) - write this down
ix. Note the new offset-I to the right(G) - write this down
d SI ope and Offset for 10 - 25 ppm
i. Leaving sensor in 9.82 ppm solution, enter 9.82 in 1s1 reference box(A).
ii. Click 1st measurement button(B). Click OK on popup when stable(C).
Add 20 ml of 100 ppmN-NO3 standard to increase solution to 23.3 ppm.
Enter 23.3 in 2nd reference box(D).
v. Click 2nd measurement button(E). Click OK on popup when stable(C).
vi. Note the new slope-M to the right(F) - write this down
vii. Note the new offset-I to the right(O) -write this down
. Compute & record new slope and offset
i. Slope-M:
1. Compute the new slope by taking the average of the two slopesyou previously wrote
down.
2. Replace the current M value in the M box(J) near the top of the field calibration window
with tiiis new computed slope.
ii. Offset-I:
1. Compute the new offset by taking the average of the two offsets you previously wrote
down.
2. Replace the current I value in the I box(K) near the ton of the field calibration window
with this new computed offset.
iii. Click OK(I) on the calibration window to save new values to sensor.
Instrumentation Northwest, Inc. www.inwusa.com infojojinwusa.com
8902 122nd Avenue NE, Kirk'land WA 98033 (425) 822-4434 Fax (425)822-8384
4620 Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc# 9B0812r2 04/10 Page13of15
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Standard Operating Procedure for the AquiStar Tempi-lion1
Smart Sensor- pH, ISE, Redox (April 2010)
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2. In-Field 1-Point Calibration
a. You will need a sample of your well water, 2 molar ammonium sulfate as ionic strength adjuster (ISA), 10
ppm N-NO3 standard. NOTE: all liquids must be at the same temperature, as must the sensor, during
calibration.
b. Preparation
i. Set Aqua4Plus to display ISE in mV.
ii. Draw water from your sample well and put 100 ml in beaker.
iii. Add 1 ml of ISA (ammonium sulfate)
iv. Place sensor in beaker and allow to stabilize
c. Take first reading
i. Using real time monitor, take a few readings with Aqua4Plus
ii. Once readings are stable, write down the mV reading (Et).
d Take second reading
i. Add 10 ml of 10 ppm N-NO3 standard
ii. Using real time monitor, take a few readings with Aqua4Plus
iii. Once readings are stable, write down the mV reading (£2).
e. Compute and record new offset
i. Take difference of mV readings from c and d above.
Q Factor
Q =
where:
AE = E2 - E,
current slope
(volume of standard) /
(volume of solution)
(volume of solution) /
(volume of standard)
S =
P =
ii. Using the formula to the right or looking up in a Q table
or spreadsheet, determine Q factor.
iii. Current concentration = Q factor * 10 ppm.
iv. Set Aqua4Plus to display ISE in ppm
v. In Field Cal window, enter Current Concentration, from step e iii., above, in 1st reference box(A).
vi. Click 1st measurement button(B). Click OK on popup when stable(C).
vii. Click Apply button(H) to move newly calculated offset-I to I box(K) near top of field cal window.
(Slope-M will not change.)
viii. Click OK(I) on the calibration window to save new offset to sensor.
Final calibration with sensor in well
i. Place the sensor in the well and allow to stabilize.
ii. In Field Cal window, enter Current Concentration, from step e iii., above, in 1st reference box(A).
iii. Click 1st measurement button(B). Click OK on popup when stable(C).
iv. Click Apply button(H) to move newly calculated offset-I to I box(K) near top of field cal window.
(Slope-M will not change.)
v. Click OK(I) on the calibration window to save new offset to sensor.
Instrumentation Northwest, Inc. www.inwusa.com infojojinwusa.com
8902 122nd Avenue NE, Kirkland WA 98033 (425)822-4434 Fax (425) 822-8384
4620 Northgate Blvd.* 170, Sacramento CA 95834 (916)922-2900 Fax (916) 648-7766
©1997-2009 by Instrumentation Northwest, Inc. Doc#9B0812r2 04/10
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Standard Operating Procedure for the AquiStar TempHion™
Smart Sensor- pH, ISE, Redox (April 2010)
TempHion: pH Well 17
I Temperature
2: ISE-Mlrue
Chennel Lebel |lSE-Nitraie
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4.00 ppm
1000 ppm
2000 'C
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Ret ppm (A)
mVf
Second Poim Cal Values
®
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Click OK when r
h ?.>-.;• stebil
(00K |
32177 mV
2572 *C
codings
zed
Cancel |
Inslrumentaban Morthwest Inc
4E30 N««hgate B)vd * 170. Sawamefito CA 953M (9»6) 922-2800 Fax (916) W8-77S6
©1997 -2009 by lns4njmsntati*nNorthw*st. me ooe*9B08t2r2 04/10
Pa0»l5oM5
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Appendix E
Laboratory Test Procedures
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USDA-ARS, National Laboratory for Agriculture and The Environment.
Method for Determination of Inorganic Anions in (Tile, River, Stream) Water & Aqueous
Solutions by Ion Chromatography
Current analytical method (1/27/2010; B.D.)
The procedure was developed from EPA method 300.1 and Dionex Application Note 154.
Equipment:
The Dionex ICS-2000 Reagent-Free Ion Chromatography (RFIC) System consists of the
following components: eluent generator, column heater housing an lonPac AS18 analytical
column (4 x 250 mm) and lonPac AG18 guard (4 x 50 mm), dual piston pump, EluGen EGC-
KOH Cartridge with CR-ATC and an anion self-regenerating suppressor (ASRS-Ultra II) in line
with a digital conductivity detector. A Dionex AS40 autosampler is used to deliver samples to
the ICS-2000. The ICS-2000 and autosampler are controlled by the Chromatography
Workstation with Chromeleon 6.5 software.
Reagents
House deionized water is run through a Milli-Q system to achieve with 18 MQ -cm resistivity or
better, filtered through 0.22 um filter and degassed for 30 minutes with helium.
Anion solutions (nitrate-N, nitrite-N, phosphate-P, chloride, fluoride, sulfate and bromide) are
purchased as 1000 ppm stocks in 125 ml volumes from Dionex. Anion solutions are stored in
the manufacturers bottles at 4° C for not more than 6 months (EPA Method 300.1). New
standards will be purchased for the ETV project.
Calibration Standards:
Calibration standards are prepared monthly by diluting the 1000 ppm stocks (described above) in
deionized water. Calibrated pippettes (Rannin) and glass volumetric flasks are used. The
concentrations for nitrate-N and nitrite-N standards are 1, 5, 10, 20, 30 and 40 ppm which covers
the range of concentrations expected for the ETV project. We have obtained linear calibration
curves with R2 of 0.998-0.999 for nitrite and nitrate over a range of 1- 125 ppm. This is in
agreement with Dionex Application Note 154 which claims linearity up to 100 ppm.
• 1.0 ppm NO3-N Standard. Dilute 0.1 ml of 1000 ppm NO3-N stock into 100 ml
deionized water.
• 5 ppm NO3-N Standard. Dilute 0.5 ml of 1000 ppm NO3-N stock into 100 ml deionized
water.
• 10 ppm NO3-N Standard. Dilute 1.0 ml of 1000 ppm NO3-N stock into 100 ml deionized
water.
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• 20 ppm NO3-N Standard. Dilute 1.0 ml of 1000 ppm NO3-N stock into 50 ml deionized
water.
• 30 ppm NO3-N Standard. Dilute 3.0 ml of 1000 ppm NO3-N stock into 100 ml deionized
water.
• 40 ppm NO3-N Standard. Dilute 1.0 ml of 1000 ppm NO3-N stock into 25 ml deionized
water.
• 60 ppm NO3-N Standard: Dilute 3.0 ml of 1000 ppm NO3-N stock into 50 ml deionized
water
A new calibration curve is prepared for each run with at least 3 replicate standards at each
concentration.. Calibration check standards (20 ppm, prepared as described above) are inserted
every 10-12 samples in an analytical run. Laboratory reagent blanks (filtered deionized water)
are included in each set of samples. We expect the calibration curve to be linear with an R2 >
0.98. Peaks for analytes of interest are integrated quantified using the Chromeleon software and
visually inspected by the operator. Results are copied to Excell files, but the original
Chromeleon files are retained on the work station.
Chromatography Conditions:
Column: AS 18 analytical column (4 X 250 mm)
Eluent: 22 mM KOH
Eluent source technology: ICS-2000 with Continuous Regenerated Anion Trap Column (CR-
ATC)
Flow rate: 1.0 ml/minute
Temperature: 30°C
Injection volume: 25 ul
Detection: Suppressed conductivity, ASRS ULTRA II, 4 mm, Auto Suppression
Recycle Mode, 87 mA current
System Backpressure: <2500 psi
Sample Run Time: 20 minutes
Under these conditions the following analytes and their respective retention times (min) are
obtained: Br (6.8), Cl (4.2), Fl (3.0), PO4 (15.7), SO4 (7.1), NO3 (7.7), NO2 (5.0), HCO3 (5.9).
Sample Storage and Preparation:
Samples are stored on ice in the field for same-day shipment to be refrigerated in the laboratory,
[1] 5-8 ml of fresh sample are filtered through 0.22 um filter into plastic scintillation vials, then
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aliquoted into Dionex 0.5 ml PolyVials, fitted with black filtercaps and analyzed; or [2] 5-8 ml of
fresh sample are filtered into plastic scintillation vials and frozen until ready for analysis (<14
days). The frozen samples are then thawed, aliquoted as described previously. If samples are
refrigerated or frozen samples are warmed to room temperature prior to analysis. Unused
samples will be refrozen or refrigerated for use as backup material if initial analysis fails QC and
reanalysis is required.
Quality Control
In general Quality Control will be assessed as described in Method 300.1, Section 9, specifically
containing the following elements. These apply only to the analysis of nitrate. For all other
analytes only the calibration standards, calibration check standards and laboratory blanks will be
used.
• Quality Control Standard. The QCS will be prepared by dissolving 0.6068 g sodium
nitrate (NaNO3, ACS grade reagent) in deionized water and dilute to 100 ml volume. To
achieve a 1000 ppm NO3-N standard. Dilute 1.0 ml of 1000 ppm NO3-N of the QCS
stock into 50 ml deionized water to make a 20 ppm QCS for analysis. A QCS standard
is included in the analysis of each batch of samples after calibration standards. If the
determined concentrations are not within 90% to 110% of the stated values, performance
of the determinative step of the method is unacceptable. The source of the problem must
be identified and corrected before either proceeding with the initial determination of
Precision and MDLs or continuing with on-going analyses.
• Initial Precision and Recovery - To establish the ability to generate acceptable precision
results, the operator shall analyze 10 replicates of a mid-range standard (20 ppm), Using
the results of the replicates compute the average percent recovery (X) and the standard
deviation (s) for the analyte. Use the following equation for the calculation of the
standard deviation.
S=( \ ZX2-(ZX)2/n)/(n-l)
• Where, n = Number of samples, x = concentration in each sample
If the results meet the acceptance criteria, system performance is acceptable and analysis
of samples may begin. If however, s and x do not meet criteria then system performance
is unacceptable. In this event correct the problem, and repeat the test.
• Method Detection Limit. The MDL will be assessed at 0.5 ppm NO3-N as described in
Method 300.1. This will be compared to the MDL reported in Dionex Application Note
154.
• Laboratory Reagent Blanks. LRB are included in each analysis and consist of filtered
deionized water.
• Laboratory Fortified Blanks. The LFB consist of deionized water containing 20 ppm
NO3-N. (Note these are identical in composition to calibration check standards). Control
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limits described for LFB are detailed in Method 300.1, p 14. These are included
approximately every tenth position in a series of sample analyses.
• Laboratory Fortified Sample Matrix. Field water samples will be divided after filtering
and aliquating into Dionex Poly Vials and stored in the refrigerator. After analysis to
determine the "background" concentration these reserved samples will be spiked with
NO3-N to achieve concentrations 2 to 3 times above background. For example a sample
containing 10 ppm NOs-N would be spiked with a highly concentrated solution to
achieve 20 ppm NOs-N with <2% change in sample volume.
Recovery (R, %) is determined as R=[Cp-CB/S] x 100, where CF and Ceare
concentrations of the fortified field samples the concentration of the un-fortified field
sample ("background"), respectively, and s is the concentration of the spike. Acceptable
control limits are 57-125% recovery.
• Field or Laboratory Duplicates. We will perform duplicate analysis on 7% of the field
samples in each analysis. Criteria for interpretation (acceptance if the relative percent
difference is ± 10%) are as stated on Method 300.1. Samples falling outside the
acceptable range will be re-analyzed and/or flagged as failing QC procedure.
• General Laboratory Procedures. Ranin pipettes are calibrated annually and
measurements are checked by weight. Laboratory balances are checked at least monthly
using standard weights. MSDS sheets are available for all reagents. Bound and
numbered laboratory notebooks are used for each project.
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